Moneypenny is one first to notice Bond's undies (7)

I haven't cracked this one yet — but the brilliant team at Fifteensquared have:

PA (abbreviation for personal assistant, for example Miss Moneypenny in the James Bond books and films) + first letter of N [otice] + TIE’S (tie is = bond is = connection is). Undies = slang shortening of “underwear”, such as women’s panties.