AbstractSurface photovoltage spectroscopy (SPS) allows for obtaining a detailed picture of the electronic structure of semiconductors. In SPS, changes in band bending at the free semiconductor surface are monitored as a function of external illumination. Surface photovoltage spectroscopy can provide detailed, quantitative information on bulk properties (e.g. bandgap and conductivity type, defect states energy, and lifetime) and can be used for complete construction of surface and interface band diagrams, including the measurement of energy levels in quantum structures. Measurements using SPS are contactless and non‐destructive. In addition, they can be performed both in situ and ex situ, at any reasonable temperature, on many semiconducting materials, at any ambient and at any lateral resolution down to the atomic scale. In this review an overview of SPS‐related theory is presented, the SPS experimental set‐up is described and applications for the characterization of a wide variety of materials and structures are presented (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)