We present photometric and spectroscopic observations of the 2009 February 2 transit of the exoplanet XO-3b. The new data show that the planetary orbital axis and stellar rotation axis are misaligned, as reported earlier by Hébrard and coworkers. We find the angle between the sky projections of the two axes to be 37.3±3.7 deg, as compared to the previously reported value of 70±15 deg. The significance of this discrepancy is unclear because there are indications of systematic effects. XO-3b is the first exoplanet known to have a highly inclined orbit relative to the equatorial plane of its parent star, and as such it may fulfill the predictions of some scenarios for the migration of massive planets into close-in orbits. We revisit the statistical analysis of spin-orbit alignment in hot-Jupiter systems. Assuming the stellar obliquities to be drawn from a single Rayleigh distribution, we find the mode of the distribution to be 13+5-2 deg. However, it remains the case that a model representing two different migration channels-in which some planets are drawn from a perfectly aligned distribution and the rest are drawn from an isotropic distribution-is favored over a single Rayleigh distribution.