Former England wing Ruaridh McConnochie was named in Scotland's 40-man squad for the Six Nations on Tuesday, with Ireland under-20 international Ben Healy also among a group of four uncapped players.
McConnochie, 31, was capped twice by England in 2019, featuring against the United States at the World Cup in Japan.
But World Rugby's eligibility rules allow a capped player to switch allegiance to another country for which they are eligible following a three-year cooling-off period.
The Bath back's change follows a similar switch by former Australia-turned-Scotland international Jack Dempsey, who made his Dark Blues debut earlier this season, with McConnochie now opting to represent the nation of his father's birth.
With fellow wing Darcy Graham injured, McConnochie could make his Scotland debut against England in their Six Nations opener at Twickenham on February 4.
"When the rule changed, we were quickly aware of who that would apply to," said coach Gregor Townsend after announcing his squad.
"In October I spent a day in Bath and caught up with Ruaridh and he told me it was his ambition to get into a Scotland squad at some stage."
Munster fly-half Healy, qualified to play for Scotland through his maternal grandparents, has been called up following an injury to Adam Hastings and will compete for the No 10 shirt with Finn Russell and Blair Kinghorn.
With Joey Carbery and Jack Crowley blocking Healy's path at provincial level, he has decided to pursue a career in Scotland and is joining Edinburgh next season.
The 23-year-old could face Ireland in the fourth round of this season's Six Nations and at the World Cup in France, with the two Celtic nations in the same pool.
"We feel he's got Test match ability," said Townsend. "His kicking game is strong, he's confident and he leads the attack well when he gets the opportunity to do that at Munster."
Experienced backs Sean Maitland and Huw Jones have both been recalled, with back-row forward Jamie Ritchie continuing as Scotland captain.
Chris Harris (Gloucester/ENG), Ben Healy (Munster/IRL), Stuart Hogg (Exeter/ENG), George Horne (Glasgow), Huw Jones (Glasgow), Blair Kinghorn (Edinburgh), Sean Maitland (Saracens/ENG), Ruaridh McConnochie (Bath/ENG), Stafford McDowell (Glasgow), Ali Price, Cameron Redpath (Bath/ENG), Finn Russell (Racing 92/FRA), Ollie Smith (Glasgow), Kyle Steyn (Glasgow), Sione Tuipulotu (Glasgow), Duhan van der Merwe (Edinburgh), Ben White (London Irish/ENG)
Ewan Ashman (Sale/ENG), Josh Bayliss (Bath/ENG), Simon Berghan (Glasgow), Jamie Bhatti (Glasgow), Fraser Brown (Glasgow), Dave Cherry (Edinburgh), Andy Christie (Saracens/ENG), Luke Crosbie (Edinburgh), Jack Dempsey (Glasgow), Matt Fagerson (Glasgow), Zander Fagerson (Glasgow), Grant Gilchrist (Edinburgh), Jonny Gray (Exeter), Richie Gray (Glasgow), Cameron Henderson (Leicester/ENG), WP Nel (Edinburgh), Jamie Ritchie (Edinburgh, capt), Pierre Schoeman (Edinburgh), Javan Sebastian (Scarlets/WAL), Sam Skinner (Edinburgh) Rory Sutherland (Ulster/IRL), George Turner (Glasgow), Hamish Watson (Edinburgh)
Coach: Gregor Townsend (SCO)