Firms in Belfast, Salford, Portsmouth, Cardiff, Derby, Bristol, Edinburgh, Newport, London and Manchester will be able to access grants worth up to £3,000 to improve their connections, with the scheme due to be extended to 12 more cities next year.
Prime Minister David Cameron said he wanted to give firms the ability to set up or locate anywhere in the UK.
The announcement is timed to coincide with the Small Business Saturday initiative promoting the firms Mr Cameron described as the "lifeblood of our economy".
The Prime Minister said: " Up to £3,000 of broadband vouchers for small business in these cities is not only a massive boost for growth in the UK, but also has the potential to bring China to Cardiff, Brazil to Bristol and the Emirates to Edinburgh in an increased export market.
"As part of our economic plan, I want to give our small businesses every possible advantage to compete in the global race - and also the flexibility to locate or set up right across the UK.
© 2013 Press Association