The theoretical concepts, experimental tools, and applications of surface photovoltage (SPV) techniques are reviewed in detail. The theoretical discussion is divided into two sections. The first reviews the electrical properties of semiconductor surfaces and the second discusses SPV phenomena. Next, the most common tools for SPV measurements and their relative advantages and disadvantages are reviewed. These include the Kelvin probe and the use of MIS structures, as well as other less used techniques. Recent novel high-spatial-resolution SPV measurement techniques are also presented. Applications include surface photovoltage spectroscopy (SPS) which is a very effective tool for gap state spectroscopy. An in-depth review of quantitative analyses, which permit the extraction of various important surface and bulk parameters, follows. These analyses include: carrier diffusion length; surface band bending, charge, and dipole; surface and bulk recombination rates; surface state distribution and properties; distinction between surface and bulk states; spectroscopy of thin films, heterostructures and quantum structures; and construction of band diagrams. Finally, concluding remarks are given.