The Cd0.6Zn0.4S/TiO2 hierarchical heterostructures were successfully fabricated by combining the electrospinning technology and hydrothermal method. The effect of calcination temperature of TiO2 on the characteristic and photocatalytic activity of Cd0.6Zn0.4S/TiO2 were investigated. The morphology, crystalinity, composition and band gap of Cd0.6Zn0.4S/TiO2 were characterized. The results indicated the optical absorption and photocataytic properties of Cd0.6Zn0.4S/TiO2 were obviously affected by the TiO2 calcination temperature. When the calcination temperature was 500°C, the Zn0.6Cd0.4S/TiO2 exhibited an enhanced photocatalytic activity for degradation of RhB under visible light.