The Scotch Whisky Association is among 29 representatives showcasing UK business.
The trip - which begins on Tuesday - is aimed at building new investment, trade and export ties with emerging markets.
They will visit South Africa, Nigeria and Kenya and meet with leading firms, policy makers and entrepreneurs.
Theresa May, who will be in the continent for her first official visit as Prime Minister, said: “Scotland’s trade outside the EU is going from strength to strength, with an increase of over half a billion pounds in exports to these markets earlier this year.
“Scotch whisky is known the world over for its quality and heritage, and I want to see Scottish industry make the most of the opportunities that lie ahead in the vibrant, emerging markets across Africa.
“That’s why I am leading this delegation to show off the UK’s unique offer to our African partners, and I am delighted that the Scotch Whisky Association will be joining me to further boost the reputation and growth of Scottish trade overseas.”
Scotland’s whisky industry supports 40,000 jobs across the UK, including 7,000 in rural areas north of the border.
Earlier this year, Scotch Whisky was registered as a trademark in South Africa, the seventh largest market by volume - with nearly 100 bottles shipped there every minute.
Exports of the spirit to the continent increased by over 13% last year, with double-digit growth in both South Africa and Kenya.
Africa accounts for just 4.5% of global exports overall, which the group says means there is room for expansion.
Karen Betts, chief executive of the Scotch Whisky Association, said: “I’m delighted to be able to join the Prime Minister on this trade delegation to Africa.
“It’s a great opportunity to showcase the heritage, craft and quality of Scotch Whisky in markets with significant potential for growth in the years ahead.
“Importing to Africa can involve a good deal of bureaucracy as well as complex tariff and non-tariff trade barriers, which tend to stifle growth.
“I hope this visit will support the industry in helping remove some of these difficulties, and help Scotch to compete on a level playing field with local products.
“I look forward to discussing these issues in Africa and with the Prime Minister and senior officials so that the UK’s largest food and drink export can continue to flourish in new markets.”