The town of Llandrindod Wells is hosting the historic occasion as bishops, clergy and lay people representing all six dioceses in the Church of Wales are locked inside Holy Trinity Church.
The election of the 13th Archbishop of Wales comes after the retirement of Dr Barry Morgan who held the position for 14 years.
His successor will be one of the six diocesesan bishops in the Church in Wales including the first female bishops Rt Rev Joanna Penberthy and Rt Rev June Osborne.
Following a time of discussion, prayer and reflection, nominations will be called for. Those nominated will then be removed from the discussions before a vote takes place.
Once a nominee receives two thirds of the votes - they will be elected Archbishop. If no one gets the two thirds, another round of nominations will take place.
A formal announcement will be made with the opening of the church doors where the successful bishop will confirm his or her election.
The new archbishop would then be enthroned at their home cathedral and take up the new role alongside their current role.
Three days are allowed for the election and if no agreement can be made, responsibility is then passed onto the Bench of Bishops.
Listen to Canon Robert Townsend from the Church in Wales talking on Premier's Inspirational Breakfast show: