Mark Webster takes the top comms role at the charity and will now set out to 'wake the sleeping giant'.
Starting on 4 February, he will be responsible for media relations, research, policy, public affairs and events.
Webster reports to CEO John Low, who joined last August from the RNID and is putting more emphasis on comms.
Low said: 'Mark will play a vital role in changing attitudes to encourage greater giving to charities and raising awareness of the giving agenda.'
At his previous role Webster worked closely with Menzies Campbell. He left when Campbell stepped down as party leader last year and he has been freelancing since.
He took the role because of his long-term support for CAF. 'Even during my journalist days, I was bewildered that CAF's profile was not higher. It is time to wake the sleeping giant,' he said.
Webster is an ex-leader writer for the EveningStandard. He has also been industrial and Africa correspondent for the FT, economics and business editor for ITN, and news correspondent for Channel Five News.
Former freelancer Mandy Pursey also started this week as head of PR. She has been the joint number two in the Sainsbury's comms team.
Pursey said: 'I was attracted to CAF because John Low thinks comms is key to the organisation's future success. In the past few years the team has declined and become quite reactive due to lack of resources. I look forward to the challenge of growing the team and turning things around.'
Webster replaces Andrew Jones, director of external affairs and policy, who has moved abroad. Pursey takes the role of Vicki Pullman, who is now head of policy and stakeholder relations.
CAF works with individuals, companies and charities to promote effective giving.