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Solar Fuels and chemicals from CO2 can be produced through two main reactions: one is CO2 photoreduction, using different catalysts and different reducing agents; the other is CO2 fixation, which is usually performed through natural photosynthesis. The research nowadays is directed on the production of fuels and chemicals with one or two atoms of carbon, for example CH4, CO, HCOOH, HCHO, CH3OH, C2H5OH, etc. The chapter aims at comparing natural photosynthesis processes and reactions with artificial photosynthesis. After taking into consideration the natural photosynthetic process, the chapter focuses on heterogeneous and homogeneous photocatalysis. Heterogeneous catalysis can be performed with semiconductors and powder catalysts. Special attention is given to TiO2 as a promising photocatalyst. Homogeneous photocatalysts are usually represented by molecular catalysts, which are dissolved in water or another solvent. Usually, homogeneous photocatalysis is performed in complex systems which are composed by: a light harvesting unit (LHU) (i.e. the photosensitizer); one catalytic site for the oxidation process, where the electrons are supplied by a sacrificial donor; one reduction site, where the electrons are transmitted to CO2. Finally, even more complex systems are represented by those based on photoelectrocatalysis. These have the main advantage to separate the oxidation and reduction reactions at the two different electrodes of the system. In principle photoelectrochemical cells can be a way to mimic artificially the working principle of natural photosynthesis.