Virgin Trains has started selling tickets for the new return service, which commences from 14 December.
The service includes an early train leaving Stirling at 05:26, arriving at London King's Cross at 10:52.
Scottish government transport minister Derek Mackay welcomed the move as "an undoubted draw for tourists, business and residents" which could bring "significant economic benefits".
He added: "It is my firm belief that using the train is also a sustainable alternative to domestic air travel, and I am delighted that those people who work between central Scotland and London will now have the option of choosing a more environmentally friendly and comfortable way of making their journeys."
David Horne, managing director at Virgin Trains, said the new services "mark a major milestone" for the firm.
The company is also creating new services between the capital and Sunderland and Leeds.
A new direct train service is to be launched linking Stirling with London.