TiO2 nanocrystals with tunable bulk/surface defects were synthesized and characterized with TEM, XRD, BET, positron annihilation, and photocurrent measurements. The effect of defects on photocatalytic activity was studied. It was found for the first time that decreasing the relative concentration ratio of bulk defects to surface defects in TiO2 nanocrystals could significantly improve the separation efficiency of photogenerated electrons and holes, thus significantly enhancing the photocatalytic efficiency.