Over a thousand people turned out to greet him in Norwich, where he began the five-day pilgrimage.
Reflecting on its significance, he said: "I think the key thing is to remember to be centred on Jesus Christ – that's why we start with prayer."
He continued: "The Church praying together and gathering together to pray is something that draws other people to faith in Christ."
The Archbishop is inviting people to join him in prayer at each stop along the way - in Coventry, London and Southwark, Truro and Chichester.
The group was then due to walk to the ruins of the old cathedral to pray for reconciliation.
The pilgrimage ends on Tuesday with Choral Evensong in the cathedral at 5:30pm.