Moneypenny is one first to notice Bond's undies (7)
I believe the answer is:
panties
'moneypenny is one first to notice bond's undies' is the definition.
I can't tell whether this definition defines the answer.
'moneypenny is one first to notice bond's' is the wordplay.
'moneypenny' becomes 'p' (I can't explain this - if you can you should believe this answer much more).
'is one' becomes 'a' (a thing is one thing).
'first to' suggests taking the first letters.
'bond's' becomes 'tie's' (both can mean a connection).
The initial letter of 'notice' is 'n'.
'p'+'a'+'n'+'ties'='PANTIES'
Can you help me to learn more?
(Another definition for panties that I've seen is " Clothes".)