Hilary Morgan died at home and had been suffering from cancer.
Archbishop, Dr Barry Morgan, thanked those who had been praying for her and the family since her illness began.
He said: "Hilary appreciated the care and concern you all showed and we were both upheld in a way I cannot describe by your prayers.
"She fought bravely over the last 20 months and never complained. She died without pain and at home as she and all of us wanted.
"All we can do now is release her into God's tender hands."
The Bishop of Swansea and Brecon, John Davies, said: "Throughout the Archbishop's ministry, Hilary had been a source of wonderful support and help to him.
"Her loss will be keenly felt and I am sure the entire Church in Wales would wish to assure the Archbishop and his family of our love and prayers as they grieve privately."