Portraits of 37 black Britons at their height of their achievements - from Naomi Campbell to Sir Trevor McDonald to Dizzee Rascal - were acquired by the gallery to be displayed run next year.
Sentamu is Britain's first black Archbishop and was appointed in 2005.
He graduated in law from Makerere University, Kampala and is an Advocate of the High Court of Uganda.
He practised Law both at the Bar and at the Bench before he came to the UK in 1974 and is an Advocate of the High Court of Uganda. He practised Law both at the Bar and at the Bench before moving from Uganda to the UK in 1974.
It is the gallery's largest acquisition of portraits of Afro-Caribbean sitters and features Line Of Duty star Thandie Newton, singer Laura Mvula, ex-footballer Les Ferdinand, musician Tinie Tempah and recently appointed editor-in-chief of British Vogue Edward Enniful.
Labour MP Chuka Umunna, Olympic gold-medallist Denise Lewis and comedian and actor Sir Lenny Henry are also included in the line-up.
Simon Frederick, who photographed the individuals for BBC Two documentary Black Is The New Black, donated the entire portfolio to the gallery.
The photographs join the National Portrait Gallery's primary collection and will be the subject of a major display in November 2018.
Dr Nicholas Cullinan, director of the National Portrait Gallery, said: "These striking portraits of black British sitters powerfully reflect the diversity and variety of contemporary British achievement in public life."
Dr Phillip Prodger, head of photographs, said: "Photographing with sensitivity and insight, Simon Frederick has made extraordinary portraits of some of the most influential Britons of our time.
"We are proud to welcome these works into our collection, where they will be seen, enjoyed, and celebrated for generations to come."
