The need for novel water treatment technologies has been recently recognised as concerning contaminants (organics and pathogens) are resilient to standard technologies. Advanced oxidation processes degrade organics and inactivate microorganisms via generated reactive oxygen species (ROS). Among them, heterogeneous photocatalysis may have reduced efficiency due to, fast electron-hole pair recombination in the photoexcited semiconductor and reduced effective surface area of immobilised photocatalysts. To overcome these, the process can be electrically assisted by using an external bias, an electrically conductive support for the photocatalyst connected to a counter electrode, this is known as photoelectrocatalysis (PEC). Compared to photocatalysis, PEC increases the efficiency of the generation of ROS due to the prevention of charge recombination between photogenerated electron-hole pairs thanks the electrical bias applied. This review presents recent trends, challenges, nanomaterials and different water applications of PEC (degradation of organic pollutants, disinfection and generation of hydrogen from wastewater).