Sylvestre was born in Sceaux, south of Paris, the third son of Israel Silvestre, the notable engraver and drawing-master to the Grand Dauphin himself. Louis was taught initially by his father, then trained under Charles Le Brun and Bon Boullogne; he completed his studies in Rome, where he met Carlo Maratta, whose work had a great influence on him. After his return to Paris, Sylvester entered the Académie de peinture et de sculpture in 1702 and was appointed professor in 1706. The main works he painted at this time were The Healing of the paralytic at the door of the Temple and the portrait of Louis XV. Friedrich August II, the prince-elector of Saxony, met Silvestre when he was in France and offered him the chance to work at the court of his father Augustus II, King of Poland. The artist accepted the offer, obtained permission from Louis XV, and set off on April 23, 1716; by 1718 he was living in Dresden. Both Augustus II and his son were great admirers of Silvestre's work, and bestowed upon him, in the space of thirty years, every honour imaginable: he was appointed first court painter, then, in 1727, director of the Royal Academy of Arts; he was ennobled in 1741, as was his brother Charles-François. During this period, Silvestre completed, with the help of his wife, Marie-Catherine Hérault, many oil paintings and frescos, either in Dresden or in Warsaw. He painted many portraits of the King and Queen, as well as those of other leading aristocrats. He was responsible for the most important works in the Palace of Dresden, notably, subjects drawn from Ovid's Metamorphoses for several ceremonial bedrooms and several ceilings. On the death of , Silvestre was made Director of the Art Academy in Dresden. During the time he remained at the court of Dresden, Silvestre was known as much for his personality and his distinguished friends, as by his artistic talents. The great number of works that came from his brush and the generosity of his patrons allowed him to amass a considerable fortune, and, having achieved financial security, he retired and returned to France. Louis XV awarded him a pension of 1000 crowns and apartments in the Palais du Louvre itself. In 1752 he was appointed director of the Academy of Paris. Louis de Silvestre died in Paris at the Palais du Louvre on 11 April 1760.
"As for art", says Mariette, "he was not a painter without merit, but his style had nothing that was new or too exciting; one saw only in him a good follower of Bon Boulogne."
Louis XIV reçoit à Fontainebleau le prince électeur de Saxe. 27 septembre 1714, Versailles museum;
Saint Benoit ressuscite un enfant, Louvre, Paris;
Entrevue de l’impératrice Amélie, veuve de l’empereur Joseph I, avec son gendre Auguste III, roi de Pologne, et sa famille, à Neuhaus, en Bohême, le 24 mai 1737, avec une infinité de portraits de personnages du temps; Large painting, 17 ft 6 ins in height, by 23 ft 9 ins long. Engraved by Francesco Zucchi, Dresden Gallery; another version of the Entrevue de Neuhaus is at the Louvre;
Portrait de la femme d’Auguste III, en princesse électorale;
Hercule poursuit Nessus, qui s’enfuit avec Déjanire, Dresden Gallery;
Auguste II, roi de Pologne, donnant la main à Frédéric-Guillaume I, Dresden Gallery;
Portrait de Christian V, roi de Danemark,Dresden Gallery;
Portrait de son frère Georges, mari de la reine Anne, Dresden Gallery;
Portrait de Georges, fils de la princesse Lubomirska, plus tard princesse de Teschen, appelé le chevalier de Saxe, Dresden Gallery;