St Mary's Cathedral in Glasgow is now taking bookings after the Scottish Episcopal Church's governing body, the General Synod, decided last month to let clergy conduct ceremonies for same-sex couples.
Provost of the Cathedral, the Very Rev Kelvin Holdsworth said: "It is hugely exciting to open up wedding services to all couples who want to get married.
"People at St Mary's were part of the campaign to allow gay and lesbian couples to get married in Scotland so it is not surprising that we would want to be able to offer such weddings in the cathedral itself."
It is expected same-sex couples will travel to Scotland from other areas of the United Kingdom in order to get married in a church.
The Very Rev Holdsworth went on to say: "We already have one booking from a couple coming up from England who can't get married in their local Church of England parish.
"We are glad to be able to welcome them and expect there will be many others who will follow them".
The General Synod's decision in June - which comes into force on Thursday - puts the Scottish Episcopal Church at odds with some other Anglican churches, which believe marriage should only be between one man and one woman.
Trustees at the landmark unanimously voted in favour of allowing same-sex weddings at the landmark, and they got the go-ahead from the Bishop of Glasgow and Galloway.