Noteworthy among its vast collection of documents are: the certificate of Leonardo's birth and baptism, signed by his grandfather Antonio, the Land Office records of his family, the notarial deeds drawn up by his father Ser Piero, a notary, and those of the trial for sodomy; the papers relevant to Leonardo's enrollment in the Company of San Luca, to the Adoration of the Magi and the Battle of Anghiari, and to his current accounts with the Hospital of Santa Maria Nuova.

Michelozzo built this refined architectural structure with three naves to the commission of Cosimo the Elder, starting in 1437. It is considered the first public library in Europe. Leonardo mentions it in the Codex Atlanticus and in the Codex Arundel, around 1480 and then around 1505.

The Library forms part of the complex of the monastery of the same name, along with Brunelleschi's church and Cronaca's Vestibule built to the project of Giuliano da Sangallo. The church contains numerous works of art by artists coeval with Leonardo and close to him: Verrocchio, Perugino, and Filippino Lippi. Leonardo mentions it in the Codex Atlanticus, around 1505.

The architecture of this library is one of Michelangelo masterpieces, realised with the collaboration of extraordinary builders such as Tribolo, the master of Pierino Da Vinci.

The library contains the bibliographic materials collected by Cosimo the Elder and Lorenzo the Magnificent that, at the fall of the Medici in 1494, were confiscated and turned over to the monks of San Marco. Giovanni de’ Medici (Pope Leo X) then moved them to Rome. They were returned to Florence in 1523 by Clement VII, who commissioned Michelangelo to build the Biblioteca Medicea Laurenziana the following year. One of the library's treasures is the Trattato di architettura civile e militare [Treatise on civil and military architecture] by Francesco di Giorgio Martini (Ash. 361), dating from 1484, with five autograph postils by Leonardo dating from around 1504.

The Laurentian Codex, Ashburnham 1299, is an incomplete manuscript copy dating from the 16th-17th century of the Libro di Pittura [Book on Painting], coming from the collection of Count Giuseppe Carlo Aurelio de’ Bossi (1758-1833).

The Ashburnham repertory includes around 2,000 manuscripts that belonged to the mathematician and bibliophile Guglielmo Libri (1809-1869), notorious for having purloined many codices from various libraries, as well as numerous papers from Leonardo 's manuscripts A and B now in Paris, including those that made up the "Codice sul volo degli uccelli" [Codex on the flight of birds] (now in the Turin Royal Library).

In the early 18th century, in Florence, three copies of the Codex Leicester were made by Francesco Ducci, "priest of San Lorenzo", the librarian of the Biblioteca Laurenziana.

The first detailed biography of Leonardo, dating from around 1540, is attributed to the Anonimo Gaddiano, also known as the Anonimo Magliabechiano. It is found in today's Biblioteca Nazionale Centrale di Firenze, which was opened to the public for the first time in 1747 under the name of "Biblioteca Magliabechiana". It originates, in fact, from the private library of Antonio Magliabechi, made up of around 30,000 volumes, left in 1714, according to his will, «to the universal benefit of the city of Florence».

Originally, the Library occupied premises in the building complex of the Uffizi. In 1935 it was moved to its present seat, built starting in 1911 to the project of the architect Cesare Bazzani and subsequently enlarged by the architect Vincenzo Mazzei. On the outside of this twentieth-century building is a medallion with a portrait of Leonardo.

In 1771 Grand Duke Peter Leopold relinquished ownership of the Medici-Lotharingian Palatine Library and ordered it united to the Magliabechiana. Since then, the Library has been further enriched by many other precious collections, including those of the former monastic libraries, expropriated subsequent to the policy of suppression of monasteries enacted by Peter Leopold and continued by Napoleon.

The Biblioteca Nazionale Centrale contains material fundamental for a knowledge of Leonardo and of the Renaissance. Among other works, there are several incomplete seventeenth-century manuscript copies of the Libro di Pittura: one coming from the Monastery of the Badia Fiorentina, two in the Magliabechiana Section, two in the Palatine, one in the Suppressed Monasteries repertory, and one coming from Vallombrosa.

It is located, along with the Biblioteca Moreniana, in Palazzo Medici Riccardi.

Among its other works it possesses an apocryphal version of Leonardo's Libro di pittura and a Confessional by Lorenzo, Leonardo's brother, a wool merchant in Florence who died in 1531. The Codex Riccardianus 2275, "Precetti della pittura di Leonardo da Vinci. Manoscritto originale di Stefanino della Bella (1610-1664)" [Precepts on painting by Leonardo da Vinci. Original manuscript by Stefanino della Bella], was published by Pagani and Grazioli in Florence in 1792.

In the "Summario" [Summary] (Ms. 1920) by Biagio Bonaccorsi, Chancery Assistant to Machiavelli, we find the plan for deviating the Arno in 1504, at the height of Riglione, toward the Stagno di Livorno, as planned by Leonardo.

It contains original instruments pertaining to the Leonardian context and extensive bibliographical documentation on his work. The numerous initiatives promoted by this Institute include major exhibitions dedicated to the genius from Vinci and his relationship with the technological achievements of the 15th century, such as "Leonardo and the Engineers of the Renaissance" and "The Mind of Leonardo".