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The alarming level of carbon dioxide (CO2) in the atmosphere has aroused immense attention due to its devastating effect of climate change. This thesis focuses on photocatalytic CO2 reduction, which converts the undesirable CO2 greenhouse gas into energy-rich hydrocarbon fuel by harnessing the clean and inexhaustible solar energy. Through opportune structural modification, p-n heterojunction construction, crystal facet and surface defect engineering at nanoscale level, the bismuth-based photocatalysts developed in this project exhibit superior performance for CO2 photoreduction into methane (CH4). Therefore, this research project is believed to pave new ways for the exploration of highly efficient photocatalysts to concurrently alleviate energy and environmental-related issues.