The countdown on the use of conventional carbon-rich fossil fuels has begun; not only due to their future depletion but mainly due to the increasing concerns on their use as energy source and raw materials in the industries, which have been the main causes of the current environmental issues and climate change. Therefore, photoelectrochemical systems for H2 production and CO2 reduction into syngas or liquid fuels are promising approaches for the transformation of the abundant sunlight into renewable, green and sustainable energy carriers. Those technologies offer the perspective advantages of creating zero-emissions fuel and reducing the atmospheric CO2 levels, restoring the natural carbon cycle.