The development of artificial photosynthetic technologies able to produce solar-fuels from CO2 reduction is a fundamental task that requires the employment of specific catalysts being accomplished. Besides, effective catalysts are also demanded to capture atmospheric CO2, mitigating the effects of its constantly increasing emission. Biomimetic transition metal complexes are considered ideal platforms to develop efficient and selective catalysts to be implemented in electrocatalytic and photocatalytic devices. These catalysts, designed according to the inspiration provided by nature, are simple synthetic molecular systems capable of mimic features of the enzymatic activity. The present review aims to focus the attention on the mechanistic and structural aspects highlighted to be necessary to promote a proper catalytic activity. The determination of these characteristics is of interest both for clarifying aspects of the catalytic cycle of natural enzymes that are still unknown and for developing synthetic molecular catalysts that can readily be applied to artificial photosynthetic devices.