More than 280,000 people have visited the "Van Gogh: Poets and Lovers" exhibition, which opened on September 14 and closes on January 19.
It is the third most successful paid exhibition in the gallery's 200-year history.
The show focuses on the Dutch painter's works created between February 1888 and May 1890 -- the two years he spent in the south of France, in Arles and Saint-Remy-de-Provence.
More than 60 works are on display, including "Starry Night over the Rhône", "Sunflowers" and "Van Gogh's Chair".
Tickets have become a hot seller. All tickets until 01:15am (0115 GMT) of the overnight session had already sold by Thursday afternoon.
"Our visitors will have the rare and special opportunity to experience Van Gogh's pictures during the night and early hours of the morning," said Gabriele Finaldi, director of the National Gallery.
They will "follow in the footsteps of artists such as Freud, Bacon and Hockney who came here during those times to take inspiration from the Gallery's collection," he added.
It is the second time the museum has stayed open overnight. The experiment was first attempted in 2012 with the exhibition "Leonardo da Vinci: Painter at the Court of Milan".
