Photocatalysis is a series of advanced light-induced redox reaction processes resulting in the degradation and mineralization of organic pollutants in the presence of oxygen and water. Due to their capability to destroy contaminants under mild conditions, photocatalytic processes have attracted considerable attention in the field of waste-water treatment. However, photocatalytic reactions using the traditional TiO2 photocatalyst suffer from low energy efficiencies under solar irradiation. This low efficiency in the utilization of solar energy lies in its incapability in absorbing visible lights and also the high recombination rate of photo-excited species in photocatalysts. In addition, difficulties in the separation of fluids from micro- or nano-scale catalysts in large scale systems substantially impact cost efficiency in practice. In this thesis, strategies are explored which address these issues in order to improve the feasibility of solar photocatalysis. Two branches of photocatalytic transition metal-oxide semiconductor materials are investigated, namely bismuth-based and silver-based multi-phase heterogeneous photocatalysts. This research is focused on the design of visible-light-active metal-oxide photocatalysts to increase the absorption of visible light and to decrease the rates of electron-hole recombination, resulting in a high photocatalytic efficiency in regards to the degradation of organic pollutants. BiVO4 powder, synthesized from freshly made potassium metavanadate was prepared via hydrothermal treatment, characterized and experimentally investigated for the degradation of rhodamine B under visible light irradiation. The crystal structures and the specific surface areas of the composites, based on BiVO4 single phase crystal structures, are discussed. A multi-phase silver species (Ag2O/Ag3VO4/Ag4V2O7) photocatalyst was synthesized by adjusting the molar ratio of silver to vanadium (Ag to V) via hydrothermal method. The stabilities of as-prepared silver species composites regarding crystal structural changes due to photocatalytic reactions are investigated. Multi-phase silver species composites assisted with graphene oxide (GO-Ag2O/Ag3VO4/AgVO3) were synthesized at room temperature, and exhibited high visible-light photocatalytic activities regarding the degradation of model organic pollutants. The effect of graphene oxide addition on the photoactivity and on the photocorrosion of silver species composites under VLI is explored. The synergistic roles of each individual phase incorporated into the multi-phase composites are discussed regarding the photocatalytic performance.