Mesoporous TiO2 with highly crystalline pore wall has an enormous potential for applications in photocatalysis, catalyst support, drug delivery, etc. However, with the sintering temperature increasing, the crystallinity of the pore wall increases while the mesopore structure tends to collapse. In this work, we presented a novel strategy for creating highly crystalline mesoporous TiO2 (MT800) by using carbon to protect the pore structure at elevated temperature. The structural characterization indicates that MT800 has highly crystalline anatase phase and processes high surface area. The photocatalysis performance was evaluated by organic degradation and the results show that MT800 has superior photocatalysis activity to the TiO2 (T800) calcined at 800°C without carbon, because of the synergies of crystallinity and mesostructure.