The photocatalytic activity of materials for water splitting is limited by the recombination of photogenerated electron-hole pairs as well as the back-reaction of intermediate species. This review concentrates on the use of electric fields within catalyst particles to mitigate the effects of recombination and back-reaction and to increase photochemical reactivity. Internal electric fields in photocatalysts can arise from ferroelectric phenomena, p-n junctions, polar surface terminations, and polymorph junctions. The manipulation of internal fields through the creation of charged interfaces in hierarchically structured materials is a promising strategy for the design of improved photocatalysts.