Polycarpou's work in movies include Evita (alongside Madonna), Oklahoma!, and De-Lovely. On stage, he was the first actor to play the role of John in the musical Miss Saigon in London. He was an original cast member of the musical Les Misérables, and has played The Phantom in Andrew Lloyd Webber's The Phantom of the Opera. He has also appeared in the UK première of The Woods by David Mamet at the Finborough Theatre, London. Television work has included The Bill, Holby City, Casualty and Waking the Dead.
In February 2006, Polycarpou appeared in EastEnders, playing Yannis Pappas, father-in-law of character Carly Wicks for 3 episodes. More recently he played a leading role in the movie O Jerusalem, released in 2007. He also starred in a short film Broken alongside Michelle Collins playing the leading role of Solomon. The film, about a Greek Cypriot immigrant family in 1960s London won several international awards. He wrote and co-directed his own short film Mad George with ex-musician and long time friend John Hoare. The film has shown at several International Film Festivals.
Recent work includes playing Gash in Bryony Lavery's play Last Easter, directed by Douglas Hodge, at the Door Theatre in Birmingham, and the leading role of Daniel Warshowsky in the musical Imagine This at the New London Theatre in 2008.
In 2010, he starred alongside Sean Bean and Charlotte Rampling in the terrorist thriller, Cleanskin which was released in 2012. He also appeared in the eighth series of Hustle for BBCTV directed by actor Adrian Lester.
Between 2010 and 2011 he appeared alongside Emma Williams and Michael Xavier in the Chichester Festival Theatre's Love Story. It later transferred to the Duchess Theatre where it had a short run.
He also worked at Chichester Festival Theatre between 24 September and 5 November 2011 - playing Beadle Bamford in Sweeney Todd (alongside Love Story producer Michael Ball as Sweeney Todd). He returned to Chichester in 2014 to star alongside Sophie Thompson in Guys and Dolls.
In 2015 he appeared in 9 episodes of the FOX TV Drama Tyrant (TV series) playing Colonel Mahmoud.
Polycarpou is a member of the Green Party and once stood for local election in the Muswell Hill ward. He is patron of the United Kingdom Thalassaemia Society and has run in the London Marathon three times.
Polycarpou is also a drama teacher and has developed a one-day workshop which he teaches in youth theatres and schools throughout the UK. He recently directed a production of the Les Misérables Schools edition for the Act Too Youth theatre in Sussex, UK. He also produced the same production with his company, Through The Stage Door, at the Paul Robeson Theatre in Hounslow in April 2010, as well as with MasterAct at the Wilde Theatre in Bracknell in July.
Polycarpou is the patron of First Stages firststages.org.uk , a musical theatre youth group based in Devizes, Wiltshire. He takes an active part in the group and regularly coaches and directs whenever he can.
Polycarpou took an active interest in the Cypriot Film Festival UK and he is also a Water Rat and has been a Director of The Royal Theatre Fund since 2011.