Mark Baulch will work from the Fareham office of Hampshire Chamber of Commerce to connect firms with an accredited network of overseas business centres and support services.
The network is being developed by British Chambers of Commerce, the government's export support department UK Trade & Investment, and the Foreign and Commonwealth Office.
Mr Baulch, who was previously an international business development manager for global book distributor Ingram Coutts, said: 'My role is to be a conduit. I will be working directly with local chamber members to put them in touch with accredited business networks abroad quickly and seamlessly.'
The aim nationally is to help double the level of annual British exports to £1trn by 2020 and raise the number of UK exporters by 100,000.
Mr Baulch's appointment follows a successful bid by Hampshire Chamber to be the lead chamber in the south east for the initiative.
As well as Hampshire, he will provide support to firms through the various chambers serving other parts of the region including Sussex.
Stewart Dunn, chief executive of Hampshire Chamber, said: 'Mark will play a vital role in building a global network of support for businesses in the south east.
'They already export all kinds of goods and services from commercial marine to IT systems.
'Firms will now be seeking to increase trade as the economy improves at home and abroad and the chamber network here and overseas is ideally placed to help them.'
During nine years at Ingram Coutts, Mr Baulch worked in sales and information services roles.
His territories included Europe, Scandinavia, Russia and the Middle East.