Photocatalytic non-oxidative coupling of methane (NOCM) is an appealing approach to produce ethane and hydrogen, however, most developed photocatalysts still suffer from low activity. Here, we demonstrate that the crystal phase engineering of TiO2 via thermal annealing of Ti metal-organic frameworks (MOFs) can afford high photocatalytic NOCM performance in a flow reactor under UV-visible light irradiation. The characterization results show that engineering the TiO2 crystal phase can improve the separation efficiency of photogenerated charge carriers and promote the formation of •CH3 intermediate, thus achieving the improved performance of photocatalytic NOCM reaction. This research provides a new perspective towards the design and construction of efficient photocatalysts for NOCM reaction.