Old English houses start to captivate member of church (8)
I believe the answer is:
anglican
'member of church' is the definition.
(member of the Church of England)
'old english houses start to captivate' is the wordplay.
'old english' becomes 'anglian' (Anglia is a historical name for England).
'houses' means one lot of letters goes inside another.
'start to' indicates taking the first letters.
The first letter of 'captivate' is 'c'.
'anglian' enclosing 'c' is 'ANGLICAN'.
(Other definitions for anglican that I've seen before include "Christian in communion with the see of Canterbury" , "Member of the Church of England" , "Relating to the C of E or similar church" , "Belonging to the Church of England" , "C of E person" .)