Lord McConnell will chair the expert panel, which has been set up by energy firm SSE to determine who should receive community benefit payments linked to green energy projects.
The power company has a policy of providing areas near renewable energy developments, such as wind farms, with £5,000 of funding per megawatt of electricity each year.
It has already invested about £13 million in community projects since 2002, and if its development plans are successful, it could invest more than £240 million in the next 25 years - including some £90 million for the new fund.
Cash grants will be available to community groups, charities and non-profit making organisations, with the fund supporting community energy developments as well as projects which promote skills and those which improve the natural or built environment.
Other panel members include Jan Bebbington, a professor of accounting and sustainable development from St Andrews University, Damien Yeates, the chief executive of training body Skills Development Scotland, Nicholas Gubbins, the chief executive of Community Energy Scotland, and SSE corporate affairs managing director Alan Young.
Lord McConnell said he was “delighted to have been asked to chair this new and exciting panel and to work alongside experts who bring with them a wealth of experience across community development, environmental sustainability and skills development”.
The former first minister added: “This fund aims to support large - potentially transformational - projects in local areas, supporting skills, jobs, community energy and environmental enhancement. This is a significant amount of money made available by SSE and I know they want us to make sure these funds are allocated effectively, making a real difference.”
The first round of funding will be for groups in the Highlands, with £325,000 available when applications open in September. This will be followed by funding for Perthshire and Dumfries and Galloway next spring.
SSE chief executive Alistair Phillips-Davies said: “Our heritage in Scotland means it is only right that we support the communities in which we operate to develop and flourish. The fund we’re launching is in addition to the sizeable sums we set aside each year for communities within the immediate area around our wind farms, for existing and new sites.
“Communities have been benefiting from SSE’s community investment since we launched our first fund in 2002, and many more will be eligible to apply for funding as new wind farms become operational. If our planned wind farms get the go-ahead, during their lifetime we expect to invest over £240 million in community projects.”