Geopolymers are ecologically-friendly inorganic materials which can be produced at low temperatures from industrial wastes such as fly ash, blast furnace slags or mining residues. Although to date their principal applications have been as alternatives to Portland cement building materials, their properties make them suitable for a number of more advanced applications, including as photocatalytic nanocomposites for removal of hazardous pollutants from waste water or the atmosphere. For this purpose, they can be combined with photocatalytic moieties such as metal oxides with suitable bandgaps to couple with UV or visible radiation, or with carbon nanotubes or graphene. In these composites the geopolymers act as supports for the photoactive components, but geopolymers formed from wastes containing oxides such as Fe2O3 show intrinsic photoactive behaviour. This review discusses the structure and formation chemistry of geopolymers and the principles required for their utilisation as photocatalysts. The literature on existing photocatalytic geopolymers is reviewed, suggesting that these materials have a promising potential as inexpensive, efficient and ecologically-friendly candidates for the remediation of toxic environmental pollutants and would repay further development.