Anatase TiO2 with specifically exposed facets has been extensively studied for maximizing its photocatalytic activity. However, most previous preparation methods involve high-pressure processing and corrosive chemicals. Few works have been conducted on hierarchical composite nanostructures assembled from well-defined TiO2 nanocrystals. Here, we report a facile method for the preparation of nitrogen-doped titanate-anatase core shell nanobelts. Anatase nanorods with specifically exposed {101} facets were obtained from a simple evaporation-induced, self-assembly (EISA) process and coupled with another semiconductor photocatalyst. The composite material with improved visible-light-harvesting ability, high charge-hole mobility, and low electron hole recombination exhibited high photocatalytic performance and stability. The results presented here will make significant contributions toward the development of delicate composite photocatalysts for photocatalytic water purification and solar energy utilization.