Significant growth in sales of seafood and whisky helped exports increase £421m (8%) in 2016.
Exports to EU countries were worth £2.3bn, up £133m, which the Scottish government said underlined the importance of European markets.
Whisky exports were worth £4bn, up £153m (4%) from 2015, while fish and seafood sales were up £156M to £759m.
Rural economy secretary Fergus Ewing said: "Since this government came into office, the value of food exports has more than doubled. Food and drink is now one of the standout success stories in our economy, increasing growth and supporting jobs across the country.
"Our produce has an excellent reputation around the world and it's clear the industry is going from strength to strength. The increased collaboration between industry and public sector and the Food and Drink Export Plan are helping this by identifying opportunities to support businesses and breaking down the barriers to trade.
"These figures show the importance of retaining access to the vital European markets, which are currently worth £2.3bn to the sector, and represent our largest export market.
"We shouldn't have to face the choice between remaining as part of the UK and the EU single market. The pursuit of a hard Brexit is a major threat to this success and these figures show why we must work to protect Scotland's place in Europe.
"Scotland's food and drink sector is in fantastic health, and next week's strategy launch will outline how we plan to support the industry to build upon this success and further grow the sector to 2030."
James Withers, chief executive of Scotland Food & Drink, said the latest export figures were "fantastic news" and a new high for Scottish food and drink".
He said: "This industry is Scotland's fastest-growing major sector. Yet we have huge ambitions to grow further.
"We are clear we want to internationalise our food industry, following in the footsteps of our greatest export, Scotch whisky. We have now doubled food exports since 2007, transforming the level of trade in growing markets like Asia.
"That is crucial to extend our footprint beyond just Europe, which is still the destination for over 70% of our food exports.
"The game-changer has been developing a national brand for Scottish produce in export markets, with industry and government working hand in hand to invest in overseas trade experts and activity. If we now further deepen that work, this success story has much further to go."
David Williamson of the Scotch Whisky Association said it was clear the Scottish food and drink was "leading in the way" in terms of the country's economic and export performance.
He added: "Scotch Whisky continues to be the most significant part of this success, with overseas shipments making up around three-quarters of total food and drink exports.
"But we need support from governments as we deal with the challenges and opportunities ahead, including Brexit."
Food and drink exports from Scotland rose to a record £5.5bn last year, government figures show.