Revd Canon Joanna Penberthy became the Bishop of St Davids during a ceremony at Llandaff Cathedral in Cardiff on Saturday.
Her appointment was the first opportunity for a woman to be elected as a bishop in the Church in Wales since the decision to allow females to become them in 2013.
She was previously Rector of Glan Ithon in the Diocese of Swansea and Brecon.
Speaking ahead of the service, Canon Jo said: "While being made Bishop is awe inspiring, I am very much looking forward to joining the people of St Davids diocese as we seek to live out and share our faith in the Risen Christ."
Archbishop of Wales Dr Barry Morgan, who retires at the end of January, said: "What matters is not gender but suitability, character, gifts and that was why Joanna was elected as bishop.
"I hope everyone will celebrate with us and support Joanna and pray for her as she embarks on this next stage in her ministry."
Bishop Joanna will be enthroned at St Davids Cathedral on February 11.