Photocatalytic reduction of CO2 into hydrocarbon fuels, an artificial photosynthesis, is based on the simulation of natural photosynthesis in green plants, whereby O2 and carbohydrates are produced from H2O and CO2 using sunlight as an energy source. It couples the reductive half-reaction of CO2 fixation with a matched oxidative half-reaction such as water oxidation, to achieve a carbon neutral cycle, which is like killing two birds with one stone in terms of saving the environment and supplying future energy. The present review provides an overview and highlights recent state-of-the-art accomplishments of overcoming the drawback of low photoconversion efficiency and selectivity through the design of highly active photocatalysts from the point of adsorption of reactants, charge separation and transport, light harvesting, and CO2 activation. It specifically includes: i) band-structure engineering, ii) nanostructuralization, iii) surface oxygen vacancy engineering, iv) macro-/meso-/microporous structuralization, v) exposed facet engineering, vi) co-catalysts, vii) the development of a Z-scheme system. The challenges and prospects for future development of this field are also present.