Donohoe will take charge of the umbrella body's 13-strong external comms function when she joins as head of campaigns and communications on 7 August.
Reporting to director of public policy Campbell Robb, she will be in charge of the NCVO's PR and campaigning strategy.
"The current government review of the voluntary sector is an opportunity for the whole sector to benefit," said Donohoe. "The NCVO's role will be to make sure all organisations are represented, not just the largest ones or the ones that have the loudest voices."
The NCVO has more than 4,700 member organisations, and sister councils spread across Wales, Scotland and Northern Ireland.
Until she left last Friday, Donohoe led the WSF's research, campaigning and public affairs teams, and was responsible for trying to improve media coverage of women's sport.
After three years at the WSF, Donohoe said she felt it was time to return to a more 'conventional voluntary sector role', and that the NCVO offered the chance to work on a number of different issues.
"After many years of campaigning for individual causes I'm looking forward to promoting the sector as a whole," she explained.
Before WSF, Donohoe worked at the Institute of Alcohol Studies in Brussels, the National Asthma Campaign and Mencap. She also helped set up HIV/Aids charity Positive Action.