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."

The 72-year-old from Ramsgate, Kent, is one of seven people to have been charged with the importation offence, which has been deemed a "relatively new phenomenon" by the National Crime Agency.
But what is the scale of the problem?
More than 100 child sex dolls have been seized in the UK as part of a special operation set up by the National Crime Agency (NCA) and Border Force.
Investigators believe the dolls, which are made to be as life-like as possible, are being imported by people who have a "sexual interest" in children.
Advertised as "adult dolls" on sites including EBay and Amazon, they are manufactured in the Far East and sent to Britain via courier, fast parcel and other delivery services.
Each doll costs around Â£800, is made of a silicon-like material and weighs as much as a child.
The NCA, which set up Operation Shiraz, says paediatricians have assessed the dolls seized to be "anatomically correct".
Since March 2016, 123 dolls have been seized, destined for 120 importers.
Seven people have been charged with importation offences, two of whom, Andrew Dobson and Dean Hall, have been convicted and sentenced.
Dobson, 49 and from Crewe, was jailed for two years and eight months. He also admitted possessing indecent images of children.
Hall, 42, from Bury St Edmunds, was given a two-year suspended term. He was in also in possession of indecent images.
Hazel Stewart, operations manager for the NCA, said: "The individuals who import this type of article - child sex dolls - have a sexual interest in children and these items are an indication of that."
She said when people have been questioned by police about the dolls some have claimed they were bought for a "joke", others say they for "companionship".
"If it was a Marks and Spencer mannequin I wouldn't be stood here," she said.
Each doll is typically packed in a brown cardboard box.  It is unclothed and the head is detached from the body with the feet and hands packaged to avoid damage.
It sometimes arrives with a "pretty pink blanket".
It is not a criminal offence to possess a child doll of this kind; the only offence which people can be charged with is importation of an obscene or indecent article.
There is no legislation to stop people manufacturing them.
"Whether they're indecent or obscene is a matter of big debate," said Ms Stewart, acknowledging that some will argue allowing people to have such dolls may stop them abusing real children.
However, Ms Stewart says there is a "gap' in the law which needs to be plugged.
"We want to look at the legislation," she said. "Child sex robots are just around the corner."
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.
[NEXT_CONCEPT]
David Turner is awaiting sentence after admitting to a court that he imported an obscene child sex doll into the UK.