Holly Cram, 29, who has amassed more than 140 caps for her country, will be involved in the Game on Scotland initiative.
The scheme, described as the official education programme for Glasgow 2014, aims to use the Games as a springboard for exploring topics such as global citizenship and health and wellbeing in schools.
In her role as an ambassador, Ms Cram, who recently qualified as a teacher and currently coaches at Dollar Academy, will talk at events such as school assemblies, award ceremonies and prize-givings.
The sports star, who plays for Glasgow Western hockey club, represented Scotland at the 2010 Commonwealth Games and is training with the intention of competing again in the 2014 Games.
She said: "I'm already seeing the effect and legacy impact the Games is having on my home city, as well as across the whole of Scotland, and the organisers have done an incredible job so far.
"I'm thrilled to be coming on board also as an ambassador for Game on Scotland, to help spread learnings around the Games, and the impact they will have on our young people will be invaluable. Youngsters will be able to see first-hand how hard work and a little self-belief can make anyone successful."
The programme involves Education Scotland, the Scottish Government, Glasgow 2014 and the city council.