Natasha Marke-Jones and Phoebe Richards struck in a stunning 2-1 win to give Wales their first victory over Scotland in more than decade.
Marke-Jones fired Wales ahead on 22 minutes in their first of a three test series in Glasgow.
Amy Brodie levelled for the hosts within two minutes but Richards, on her 75th appearance, netted the vital winner in the second-half.
Coach Kev Johnson’s side have risen six places in the world rankings to 26th but were still facing a Scottish side nine spots ahead of them in 17th.
There are two further games on Sunday and Monday as the squad continue their preparations for the European Women’s Championships II in Cardiff in August.
Beth Bingham, 22, celebrated winning her 50th cap for Wales while Emily Rowlands was handed her debut having been promoted from the Challenger squad.