NH2-MIL-125(Ti) crystals were prepared by a solvothermal method. By varing the ratios of N,N-dimethylformamide (DMF) and methanol (MeOH) in the synthesis system, NH2-MIL-125(Ti) crystals exhibited circular plate, decahedral or octahedral morphology. XRD, SEM, FT-IR and BET characterization techniques were used to study the physical properties of NH2-MIL-125(Ti) crystals with different morphologies. Then these crystals were used in the photocatalytic oxidation of cyclohexane under visible light irradiation. The structure-activity relationship between catalytic performance and crystal plane was explored. Results showed that the main reaction of selective oxidation of cyclohexane to target products cyclohexanol and cyclohexanone occurs in the {110} crystal face family of NH2-MIL-125(Ti) crystal, whereas the {101} crystal face family is mainly to further oxidize cyclohexanol and cyclohexanone into COx.