N-doped titania hollow mesoporous microspheres (N-THS) with good spherical morphology were prepared via LBL self-assembly and calcination method by using triethylamine as nitrogen source. The structure and photocatalytic property of N-THS were investigated with XRD, XPS and UV-Vis DRS. Results show that parts of N inserted into the TiO₂ lattice and replace parts of O, thereby change the chemical state of Ti and O in the lattice. After calcination in a temperature range 400-600℃, anatase TiO₂ was obtained for the N-THS, while rutile TiO₂ appears when calcination at temperatures up to 700℃. The particle size of TiO₂ increases with the increasing calcination temperature. N-THS exhibit strong photoabsorption ability in the visible light region with a clearly red-shifted absorption spectral band. Correspondingly N-THS show good degradation efficiency for methyl orange solution, and along with the decreasing calcination temperature the visible light region absorption ability and the degradation efficiency of N-THS may be enhanced. The degradation efficiency of N-THS calcinated at 400℃ can reach 93.5% after 80 min light irradiation.