The Royal Clarence Hotel on Cathedral Green is said to be close to collapsing as the fire, which began early on Friday morning, continues to burn.
Premier telephoned Exeter Cathedral on Saturday morning to hear that clergy were in a briefing with fire chiefs.
The cathedral has also played a significant part in relaying safety announcements to the community, telling people to follow the advice of emergency services and avoid the area until it is clearly safe.
.@DSFireUpdates doing great work around Cathedral Green right now. Thank you!
— Exeter Cathedral (@ExeterCathedral) October 28, 2016
2/2 Our thoughts and prayers are with all those who are affected by the incident and those working to bring the fire under control
— Exeter Cathedral (@ExeterCathedral) October 28, 2016
It was forced to cancel some services while the area was deemed too dangerous.
The cathedral's Solemn Eucharist on Friday also included prayers for those affected by and involved in fighting the fire.
Canon Anna Norman-Walker, from Exeter Cathedral, told Premier: "It's a beautiful ancient building and we've got a very close relationship with it.
"It's owners have been great supporters of the Cathedral over many years but also lots of people who stay at the Royal Clarence come to visit the Cathedral as tourists, many many come to worship with us, and a number of people who worship with us are on the staff there.
"So yes, it's a hugely significant part of our story in Exeter."
There are no reports of injuries or deaths from the fire (below).
#exeterfire picture taken at 05:20 just as we got evacuated from hotel. pic.twitter.com/x3AC5GBWOb
— 6ix Engineering (@6ixeng) October 28, 2016
Exeter Cathedral's prayer for the city:
Merciful and loving God
We bring before you those working tirelessly to bring the fire on our beloved Cathedral Green under control.
Grant them all the skills they need at this time.
We ask that you give strength and resilience to our Firefighters, Police and those supporting them.
We pray for the Residents in their anxiety and those whose businesses are in jeopardy.
May they know your comfort and peace.
Through Jesus Christ our Lord.
Amen.
Listen to Premier's Aaron James speaking to Canon Anna Norman-Walker: