Pair going round Brazilian city earlier (5)
I believe the answer is:
prior
'earlier' is the definition.
(synonyms)
'pair going round brazilian city' is the wordplay.
'pair' becomes 'pr' (abbreviation).
'going round' is an insertion indicator (some letters go around others).
'brazilian city' becomes 'Rio' (Rio de Janeiro).
'pr' placed around 'rio' is 'PRIOR'.
(Other definitions for prior that I've seen before include "Deputy head of an abbey" , "More important" , "English poet" , "head of a house of friars" , "Already arranged" .)