Appear to spy on James Bond’s boss (4)
I believe the answer is:
seem
'appear' is the definition.
('seem' can be a synonym of 'appear')
'spy on james bond's boss' is the wordplay.
'spy' becomes 'see'.
'on' says to put letters next to each other.
'james bond's boss' becomes 'm' (M is the head of MI6 in the James Bond series).
'see'+'m'='SEEM'
'to' acts as a link.
(Other definitions for seem that I've seen before include "Appear, give impression of being" , "Appear, look" , "Come across as" , "Appear to the eye" .)