The two characters have very diverse personalities and proceedings. Personally, I believe Odysseus is the wittier character. He is faced with far more challenges than Penelope, and even though he does make mistakes, you must remember he is merely human. I think the following quote best supports my thesis, "When times are easy, people are nice and wise, but when times get rough your true personality is revealed." I don't think Penelope was ever faced with a hardship that ever challenged her well-being or that of others. On the other hand, Odysseus encountered many of these defying phases.
Both gods and humans admire Odysseus for his extraordinary wisdom. It's one of his key personality traits. It's also the attribute that attracts Athena. Odysseus also proclaims his wisdom during his encounter with the Sirens. He plugs his men's ears and then ties himself so the beautiful Sirens wouldn't lure him into death.
Also, not anyone can endure such a long and strenuous journey. A major factor that contributed to the well being of Odysseus is his smooth personality. He knows what to say and when to say it. Meanwhile, Penelope's greatest hardship was having to put up with the nuisances in her household, and for a great deal of time nothing was done about this. Not portraying half as much wisdom as Odysseus, I think Odysseus proves himself to be the wiser character.
In conclusion, I believe Odysseus is the more intellectual character in The Odyssey. Like I mentioned earlier he was faced with far more challenges than Penelope. Also Odysseus' character is better developed and portrays more positive traits. If Athena- a god, thought Odysseus was wise, I believe he was wiser then he had imagined or the reader had contemplated. If Athena thought it was worthwhile her time to help a human, I'm guessing she had many reasons to do so. And as I mentioned, Odysseus' wisdom attracted her, need...