Over the past decades, CO2 greenhouse emission has been considerably increased, causing global warming and climate change. Indeed, converting CO2 into valuable chemicals and fuels is a desired option to resolve issues caused by its continuous emission into the atmosphere. Nevertheless, CO2 conversion has been hampered by the ultrahigh dissociation energy of C=O bonds, which makes it thermodynamically and kinetically challenging. From this prospect, photocatalytic approaches appear promising for CO2 reduction in terms of their efficiency compared to other traditional technologies. Thus, many efforts have been made in the designing of photocatalysts with asymmetric sites and oxygen vacancies, which can break the charge distribution balance of CO2 molecule, reduce hydrogenation energy barrier and accelerate CO2 conversion into chemicals and fuels. Here, we review the recent advances in CO2 hydrogenation to C1 and C2 products utilizing photocatalysis processes. We also pin down the key factors or parameters influencing the generation of C2 products during CO2 hydrogenation. In addition, the current status of CO2 reduction is summarized, projecting the future direction for CO2 conversion by photocatalysis processes. © 2024 Wiley-VCH GmbH.