As already mentioned, keylogger is probably your best bet.
Or he could try a little social engineering; most people set a very weak reminder question, which will allow you to reset the password on inputting the correct answer. So given that your mate should know his wife fairly well, it may not be very difficult for him to guess the correct answer; or he could just drop in the required question into conversation..... "so what was your first pets name, darling??". Precisely the reason I never answer those seemingly innocuous forum posts (favorite film/favourite food/favourite tv show etc).
Ok, so this method is not as subtle as a keylogger as the password will remain reset so wifey won't be able to login herself afterwards. But tbh, most people simply put this down to it being a free email account, and will reset themselves like nothing has happened. Ok for a quick fix I spose.
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