Daniel signed with the Kansas City Chiefs on March 12, 2013. For 2013, he was secured as the backup to Alex Smith. In Week 14 of the 2013 NFL season, Daniel played against the Redskins and was 1 for 3 in passing with an interception. The Chiefs won, 45–10. In Week 17, with the Chiefs locked into the #5 seed in the playoffs, Daniel started his first regular-season NFL game, a 24–27 overtime loss to the San Diego Chargers, going 21/30 for 200 yards and one touchdown pass, while rushing for an additional 59 yards. His final 2013 stats were 248 yards, one touchdown, and one interception.