Frenchman Pic has spent the last year with Marussia, impressing in what has been his debut campaign.
Caterham, however, have not confirmed whether Vitaly Petrov or Heikki Kovalainen is departing, although the smart money is on the latter.
Pic, 22, brings with him considerable financial backing given his father owns a lucrative trucking company in France.
Such funds will aid Caterham in their bid to move up the grid given the team has yet to score a point in their three years in Formula One.
With Pic's appointment it now seems certain Marussia will confirm Max Chilton as their second driver for 2013, ensuring there will be four Britons on the grid next season.
On his appointment, Pic said: "It is clear the team has great ambitions for the future.
"The investments already made and the decisions taken in the last few months show how committed the shareholders are to succeed and demonstrates their willingness to keep going forward.
"I am very excited about starting my second year in F1 with a team that has so much potential.
"Caterham has everything in place to help it move into a position to fight with a number of teams ahead.
"I know how determined the team is to keep progressing and I am looking forward to playing my part in helping them move up the grid."
Team principal Cyril Abiteboul is convinced Pic can help the team grow and progress.
Abiteboul said: "We are all looking forward to working with a young driver who has clearly shown in his first season in F1 that he has the pace, racecraft and demeanour to help us achieve our goals.
"Throughout the 2012 season we have been monitoring the progress Charles has made, challenging us on several occasions in qualifying, and it is clear he is a special talent.
"As the year has progressed he has performed extremely well against a very experienced team-mate (Timo Glock) and we are looking forward to seeing him develop further within the environment we will provide in 2013 and beyond."