TiO2 has aroused considerable attentions as a promising photocatalytic material for decades due to its superior material properties in several fields such as energy and environment. However, the main dilemmas are its wide bandgap (3–3.2 eV), that restricts the light absorption in limited light wavelength region, and the comparatively high charge carrier recombination rate of TiO2, is a hurdle for efficient photocatalytic CO2 conversion. To tackle these problems, lots of researches have been implemented relating to structural and material modification to improve their material, optical, and electrical properties for more efficient photocatalytic CO2 conversion. Recent studies illustrate that crystal facet engineering could broaden the performance of the photocatalysts. As same as for nanostructures which have advantages such as improved light absorption, high surface area, directional charge transport, and efficient charge separation. Moreover, strategies such as doping, junction formation, and hydrogenation have resulted in a promoted photocatalytic performance. Such strategies can markedly change the electronic structure that lies behind the enhancement of the solar spectrum harnessing. In this review, we summarize the works that have been carried out for the enhancement of photocatalytic CO2 conversion by material and structural modification of TiO2 and TiO2-based photocatalytic system. Moreover, we discuss several strategies for synthesis and design of TiO2 photocatalysts for efficient CO2 conversion by nanostructure, structure design of photocatalysts, and material modification.