The new appointments include politicians, journalists, and business leaders and will work with the NCS executive leadership team to "make sure as many teenagers as possible get to experience NCS".
They include Labour peer Lord Alli, Liberal Democrat peer Baroness Floella Benjamin and Conservative peer Baroness Brady of Knightsbridge, as well as former troubled families tsar Dame Louise Casey, journalist Robert Peston, the chief executive of Barnardo's Javed Khan, and YouTube entrepreneur Jamal Edwards.
The NCS first launched in 2011, initially to a few thousand young people, but provision has been expanding each year, with the government setting aside around £1.2bn to deliver NCS up to 2020.
However, NCS participation has struggled to keep pace with targets, and, in February, the Department for Culture, Media and Sport revised its aim to grow NCS participation by 2020/21 from 360,000, which had been in the Cabinet Office's single departmental plan, down to 247,000.
Chair of NCS patrons, former Prime Minister David Cameron, said: "I'm so proud to welcome such an inspirational group of individuals to the NCS patrons board.
"These people already make a huge contribution to our country in media, education, business, sport, music, politics and the armed forces.
"By investing in our young people - helping them, through NCS, to become confident, resilient, tolerant and happy adults - they will be make an even bigger contribution still. I can't wait to start working together."
The National Citizen Service was placed on statutory footing earlier this year when the National Citizen Service Act became law, with the NCS Trust, which co-ordinates the programme, given Royal Charter status.