Carwyn Jones hailed figures showing exports from Wales increased by £1.5bn over the past year to £14.8bn.
Wales exported most to the United States, followed by Ireland, the United Arab Emirates, Germany and Holland.
The most popular Welsh export was machinery and transport equipment, worth £6bn.
Mr Jones said: "At the start of 2013 I set out the most extensive programme of trade missions since devolution.
"Today's figures clearly demonstrate the overwhelming success of our approach, with companies in Wales benefitting from substantial increases in exports to every major trading market.
"Today's figures add to the growing list of economic indicators that show the Welsh economy clearly outperforming the rest of the UK."
Welsh Conservatives welcomed the figures, whilst pointing out that exports were "rising from a low base".
Shadow Business Minister William Graham said:  "Welsh businesses have a positive story to tell in many of the products and services on offer, but we need the Welsh Labour government to improve the way it markets Wales to maximise potential gains to the Welsh economy.
"The Welsh government needs to properly develop a Welsh identity brand and to ensure better liaison with UKTI (UK Trade International) with its world wide contacts and experience.
"While this long-awaited progress is welcome after 15 years of successive Labour governments, Welsh ministers must not get complacent and should redouble their efforts to secure economic growth and make Wales a more prosperous nation."
Exports from Wales are up more than 11%, outperforming the rest of the UK whose exports rose by just 0.4%, the first minister has said.