Stewart will sing in front of around 40,000 people - and a global television audience - on the opening night of the Games at Celtic Park on July 23.
Joining Stewart will be Scottish singers Susan Boyle and Amy MacDonald and violinist Nicola Benedetti.
Glasgow 2014 chief executive David Grevemberg said: "We have always said that the opening ceremony will present Glasgow and Scotland to a global audience.
"But when we got to welcome an iconic talent like Rod Stewart it takes the excitement and anticipation for the opening ceremony to a whole new level.
"We will also be welcoming internationally renowned and acclaimed artists Susan Boyle, Nicola Benedetti, Amy MacDonald and Julie Fowlis on the night.
"They will join the thousands of people who are part of our cast for a unique celebration of the host city and nation which will not only welcome the athletes to Glasgow for the Commonwealth Games, but which will also be seen and enjoyed across the world."