Leonardo: Painter at the Court of Milan focuses on his formative years as a court artist in the 1480s and 1490s.
It features nine paintings and many more drawings by the legendary artist.
The paintings include his acknowledged masterpiece The Lady with an Ermine and two versions of The Virgin of the Rocks, hanging together for the first time.
The Portrait of a Musician, La Belle Ferronniere and Salvator Mundi - only recently authenticated as a Da Vinci - are also featured.
These 'once in a lifetime' exhibitions are becoming part of everyday life. But this one really is something special.
Seven out of the nine Leonardo da Vinci paintings on display have never been shown publicly in this country before. It is the first - and quite possibly the last - time that the Louvre's The Virgin of the Rocks (1483-86) has ever left the French museum.
For me, the unfinished St Jerome (1482) is a highlight. Lent by the Vatican, it exemplifies the renaissance artist's remarkable compositional skills, exceptional draughtsmanship and intricate painting technique.
Da Vinci primed the wooden panels on which he painted with a white paint, over which he would apply outline drawings and further, thin layers of paint.
The effect is to create pictures that not only have a three dimensional quality, but also a glowing inner light. They might be over 500 years old, but they looked pretty modern to me.
Members of the press got their chance to inspect the exhibition on Tuesday and have been lavish in their praise.
"It's the hottest ticket in town," wrote Richard Dorment in the Daily Telegraph in his four-star review.
"London's latest blockbuster art show confirms Leonardo da Vinci as a Renaissance rock star," opined Jill Lawless in the Huffington Post.
The collection of drawings, writes the Los Angeles Times' Culture Monster, "comprise an extraordinary show within a show".
The Arts Desk's Fisun Guner, meanwhile, described the exhibition as "unmissable", saying it would "do much to increase your engagement with this great master of the High Renaissance".
The National Gallery is limiting visitor numbers to the exhibition in an attempt to prevent large crowds detracting from the viewing experience.
Admissions will be fixed at 180 every half hour - 50 fewer people than the gallery is legally allowed to let in.
Even so, the audio guide accompanying the exhibition frequently advises visitors to "step back" from paintings to allow other art lovers a better view.