Section of libretto's captivating in opera (5)
I believe the answer is:
tosca
'opera' is the definition.
(I've seen this before)
'section of libretto's captivating in' is the wordplay.
'section of' indicates a hidden word.
'TOSCA' is hidden within 'librettos captivating in'.
(Other definitions for tosca that I've seen before include "One of Puccini's 19" , "title role" , "musical work" , "Ascot (anag) - operatic heroine" , "18 [OPERA]" .)