In this study, the novel mixed-phase TiO nanocrystals (s-TiO) with nearly equivalent anatase/rutile ratio were fabricated in the reagent of sec-butanol at the relatively low temperature of 80 °C by using a facile one-step condensing reflux method. The photocatalytic water splitting hydrogen production performance of s-TiO nanocrystals is close to that of commercial TiO (P25), and its photocatalytic degradation performance is about four times that of P25. The energy-level staggered interfaces and surface bridged hydroxyl groups significantly increased due to the anatase/rutile mixed-phase crystal structure and high specific surface area, which might generate the synergistic effect for the improvement of photocatalytic degradation.