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One of the promising renewable energy sources is converting CO2 into useful chemical fuels; it will help to overcome both energy supply and global warming issues. Among various methods for CO2 reduction, photoelectrochemical (PEC) CO2 conversion is the most promising and easy method so far because it can be useful to control thermodynamics and kinetics of CO2 reduction reaction for product selectivity and fast reaction kinetics by mimicking natural photosynthesis without high input energy cost. However, it has some limitation factors that create difficulties for widespread utilization. The detection of CO2 products and intermediates on a small scale is another challenging part in this field. The small amount of the CO2 product can be further oxidized or evaporated, which could be difficult to be detected. Therefore, an in situ technique is a good approach to study the proper reduction mechanism during the CO2 reduction process. This review starts with basic concept of solar to fuel (STF) conversion by CO2 reduction and covers various aspects related to photoelectrochemical CO2 reduction. This main theme is completely depending on important parameters such as photoanode materials, photocathode materials, electrolyte solutions for photoelectrochemical CO2 reduction with the most important in situ measurement techniques for product analysis.