The 34-year-old prince - who followed in the footsteps of his late mother in becoming patron of the homeless charity - joined 420 guests at the London event in the grounds of Kensington Palace, which was hosted by Jonathan Ross and featured performances from Ellie Goulding, Craig David and Dirty Vegas.
Phil Collins had also been due to sing, but he pulled out as he had been advised not to travel due to health concerns, and so he sent in a recorded video message instead and Conor Maynard stepped into perform his classic track about homelessness, 'Another Day in Paradise'.
A spokesman for Centrepoint said: "He's very sad not to be here tonight, but we hope to work with him again soon.
"Phil's song 'Another Day in Paradise' is an iconic song which woke up the world to the issue of homelessness. Nights like tonight are pivotal to raise the money so that young people can leave Centrepoint and homelessness behind."
Ahead of the gala and awards ceremony, William also attended a private reception to meet with Centrepoint supporters and young people.
The awards that were given out, across five categories, recognised the success of young people who have experienced homelessness but overcome their difficulties with the help of the charity.
Guests at the event - which cost between £1,000 and £5,000 a ticket - included Dame Joan Collins, William's cousin Princess Beatrice, soccer star John Terry, Jamie and Louise Redknapp and Chic frontman Nile Rodgers.
Seyi Obakin, Centrepoint chief executive praised William's involvement in the charity ahead of the event.
He said: "We were his very first patronage and I have not seen him at all - at any other time - more committed than he is now to see youth homelessness ended.
"That's a tough call, a big vision - but we believe it can be done."