The paper reviews the history, the present status and possible future developments of photovoltaic (PV) materials for terrestrial applications. After a brief history and introduction of the photovoltaic effect theoretical requirements for the optimal performance of materials for pn-junction solar cells are discussed. Most important are efficiency, long-term stability and, not to be neglected, lowest possible cost. Today the market is dominated by crystalline silicon in its multi crystalline and monocrystalline form. The physical and technical limitations of this material are discussed. Although crystalline silicon is not the optimal material from a solid state physics point of view it dominates the market and will continue to do this for the next 5-10 years. Because of its importance a considerable part of this review deals with materials aspects of crystalline silicon. For reasons of cost only multicrystalline silicon and monocrystalline Czochralski (Cz) crystals are used in practical cells. Light induced instability in this Cz-material has recently been investigated and ways to eliminate this effect have been devised. For future large scale production of crystalline silicon solar cells development of a special solar grade silicon appears necessary. Ribbon growth is a possibility to avoid the costly sawing process. A very vivid R&D area is thin-film crystalline silicon (about 5-30 mu m active layer thickness) which would avoid the crystal growing and sawing processes. The problems arising for this material are: assuring adequate light absorption, assuring good crystal quality and purity of the films, and finding a substrate that fulfills all requirements. Three approaches have emerged: high- temperature, low-temperature and transfer technique. Genuine thin-film materials are characterized by a direct band structure which gives them very high light absorption. Therefore, these materials have a thickness of only one micron or less. The oldest such material is amorphous silicon which is the second most important material today. It is mainly used in consumer products but is on the verge to also penetrate the power market. Other strong contenders are chalcogenides like copper indium diselenide (CIS) and cadmium telluride. The interest has expanded from CuInSe/sub 2/, to CuGaSe/sub 2/, CuInS/sub 2/ and their multinary alloys Cu(In,Ga)(S,Se)/sub 2/. The two deposition techniques are either separate deposition of the components followed by annealing on one hand or coevaporation. Laboratory efficiencies for small area devices are approaching 19% and large area modules have reached 12%. Pilot production of CIS-modules has started in the US and Germany. Cadmium telluride solar cells also offer great promise. They have only slightly lower efficiency and are also at the start of production. In the future other materials and concepts can be expected to come into play. Some of these are: dye sensitized cells, organic solar cells and various concentrating systems including III/V-tandem cells. Theoretical materials that have not yet been realized are Auger generation material and intermediate metallic band material.