Titanate/N-doped anatase composite hierarchical microspheres have been obtained by calcination treatment of NH4-titanate hierarchical microspheres at proper temperatures. The phase structure is dependent on the calcination temperature and varies from titanate to anatase with increasing calcination temperature, with the heterophase in-between. The composite structure is verified by the results of XRD, visible and UV Raman spectra. The titanate/N-doped anatase composite sample calcined at 300 A degrees C for 1 h exhibits enhanced activity in the degradation of Rhodamine B under visible light irradiation compared to the other samples. The enhanced activity can be ascribed to the synergistic effect of titanate and N-doped anatase.