He added: “This offers a sustainable travel option whilst also boosting economic growth.
“We’re proud to champion Scotland and look forward to providing the unique Lumo service to even more customers from this week.”
The service leaves Queen Street and includes stops at Falkirk High, Edinburgh Haymarket, Edinburgh Waverley, Morpeth, Newcastle and Stevenage before reaching London King’s Cross.
Scotland nationalised its rail services in April 2022, while nearly all in England are to be taken into public ownership by 2027.
However, Lumo runs on an “open access basis,” meaning it sets its own fares and receives no taxpayer-funded subsidies.
Paul Tetlaw from sustainable transport group Transform Scotland, said he hoped the new services would convince some travellers to choose rail over flying to London.
He added: “There is a significant market of people who currently drive or fly to the north east of England and London who now have the opportunity to switch to the train.
“The new services soon to be launched from Stirling will help to build on that modal shift to rail.”
He said he hoped the new connection would help ferry people to Glasgow for the 2026 Commonwealth Games.