<p>The intensifying concerns over global energy consumption and climate change, driven predominantly by anthropogenic CO₂ emissions, necessitate the advancement of sustainable carbon-neutral technologies. Photoelectrocatalytic CO₂ reduction, which synergistically integrates solar energy harvesting photocatalysis with the controllable effectiveness of electrocatalysis, has emerged as an optimistic pathway to transform CO₂ into valuable chemicals and fuels under mild conditions. This review methodically summarizes the fundamental principles, detailing critical steps from light absorption to surface redox reactions. The objective of this review is to comprehensively analyze current advances in Cu-based materials, which are uniquely positioned as catalysts due to their ability to facilitate multi-electron transfer and produce various hydrocarbons and oxygenates. We critically evaluate the performance of numerous Cu-based photoelectrodes and their hybrid nanostructures by benchmarking crucial parameters, like a faradaic efficiency of 63.3% for C₂ products and 47.4% for C₂₊ oxygenates. Additionally, the discussion summarizes future mechanistic pathways for significant products like HCOO^–, CH₄, and C₂H₄, correlating the local environmental and oxidation state of Cu active sites with experimental findings as well as a theoretical view. Despite substantial advancement, challenges such as poor product selectivity, competing hydrogen evolution, and limited long-term stability persist. This review also identifies tactical interventions, such as heteroatom doping, heterojunction formation, and application of a protective overlayer. Ultimately, this review provides future perspectives emphasizing the need for <i>in-situ/operando</i> characterization, rational design of tandem catalyst systems, and integration with scalable solar fuel production.</p> Graphical Abstract <p></p>