Morag Macdonald, who has never worked in the sector before, joins from internet company AOL where she was UK chief financial officer. She begins work in the newly created post at the start of July on a salary of ?xA3;70,000.
Joint directors in the voluntary sector such as those overseeing both fundraising and communications are common, but a finance director with responsibility for developing commercial opportunities for the charity is a first.
Macdonald has been given a remit to increase the charity's income through investments, commercial activities and strategic partnerships.
Guide Dogs has endured a stormy time financially over the past year.
A fall in the stock market forced the charity to spend ?xA3;20 million of its reserves, and the foot-and-mouth outbreak cost ?xA3;2 million in lost fundraising income.
Guide Dogs' chief executive Geraldine Peacock is a member of the UK Social Investment Taskforce and has championed the concept of charitable investment in community development finance institutions (CDFIs), which offer large charities the opportunity in make profitable investments while at the same time furthering their aims.
"In today's competitive world, charities need to make their funds work harder and smarter. While traditional fundraising will always be vital, they also need to add the words earn, enterprise and invest to their vocabularies if they want to secure financial sustainability and achieve their charitable objectives," said Peacock.
"This is why Guide Dogs is leading the way in the charity sector by appointing a business finance specialist to develop new investment and commercial opportunities in addition to looking after traditional financial management."
Macdonald replaces Andrew Herbert, who was Guide Dogs' interim finance director for more than a year.