Gabriele Finaldi has been appointed the new head of the National Gallery, replacing Nicholas Penny who announced his retirement last year.
The 49-year-old is currently deputy director for collections and research at the Prado museum in Madrid.
Finaldi was a curator at the National from 1992 to 2002, where he was responsible for the later paintings in the Italian and Spanish collections.
He said he was "deeply honoured" to take on the directorship.
"This is a world-class collection in a world-class city," he continued.
"I eagerly look forward to working with the trustees and the staff to strengthen the gallery's bond with the public and its international standing."
Finaldi, who has been at the Museo Nacional del Prado since 2002, will take up his new position on 17 August.
Born in London, he studied art history at Dulwich College and then at the Courtauld Institute of Art, where he studied 17th Century painter Jusepe de Ribera.
During his stint at the National he curated various exhibitions, including Spanish Still Life from Velazquez to Goya (1995), Discovering the Italian Baroque: The Denis Mahon Collection (1997), and Orazio Gentileschi at the Court of Charles I (1999).
Finaldi said he planned to develop an "exciting" exhibition programme at the gallery.
Analysis: Will Gompertz, BBC Arts editor
Gabriele Finaldi will re-join a National Gallery that is outwardly on reasonably good form, having presented critically-acclaimed exhibitions like the recent Late Rembrandt show, while also boasting high visitor numbers.
Internally though, it is not a happy ship. There has been anxiety among employees about recent restructures, and an on-going series of strikes by front-of-house staff, whose jobs are threatened by the proposed outsourcing of their roles to a private contractor.
Dr Finaldi is familiar with the pains and strains brought about by the sort of modernisation programme the National Gallery is currently undertaking - having overseen a similar process at the Prado.
He will start with the staff largely on his side, having won many friends in his previous stint at the gallery. The trick will be to keep them happy, while delivering more money-spinning blockbusters, without losing sight of the free-to-see collection displays.
Mark Getty, chair of the gallery's trustees, expressed his delight at the appointment, which had been rumoured for some time.
"As co-director of the Prado he has been responsible for a range of successful and complex projects and he will bring considerable experience to the Gallery," he said of Finaldi.
"We are absolutely delighted that he has accepted the post."
Miguel Zugaza, director of the Prado, praised Finaldi's contribution to the modernisation of the museum and said he hoped his appointment would further strengthen ties between the institutions.