The 22-year-old Frenchman has earned recognition for his performances relative to experienced team-mate Timo Glock at Marussia this season. His best results to date are 15th places in Melbourne and Valencia.
Caterham team boss Cyril Abiteboul said Pic had impressed him while challenging his cars with the Marussia.
"We are thrilled that Charles has decided to join us for his second season in F1 and beyond," said Abiteboul.
"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 that Charles has made, challenging us on several occasions in qualifying, and it is clear that he is a special talent.
"As the year has progressed he has performed extremely well against a very experienced team-mate and we are looking forward to seeing him develop further within the environment we will provide in 2013 and beyond."
Although Marussia is now ahead of Caterham in the constructors' championship and has closed on the Anglo-Malaysian team on-track in late-2012, Pic is still confident his new squad has the better long-term potential.
"It is clear that the team has great ambitions for the future," he said. "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."
Pic added: "I am very excited about starting my second year in F1 with a team that has so much potential. Caterham F1 team 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."
Both Caterham's current race drivers Heikki Kovalainen and Vitaly Petrov face uncertain futures, with the Finn admitting in Brazil on Thursday that his chances of a 2013 F1 seat now appeared slender.
Pic was promoted from the Marussia reserve role to a race seat this season, having previously been a race-winner in GP2 and Formula Renault 3.5. Current Marussia test driver Max Chilton is expected to take Pic's current drive next year.