In this paper a number of optical spectroscopic methods for investigating surface electronic structure are discussed, including reflectance techniques, ellipsometry, surface photoconductivity and surface photovoltage spectroscopy. In addition to electron scattering techniques and UV-photoemission, optical spectroscopic methods have contributed much in recent times to the understanding of electronic surface states on solids. A discussion and comparison is given of the nature and significance of information obtained by these methods and exemplary experimental results are presented to illustrate the contribution of the optical techniques to the present knowledge about surface states. The relation between information obtained from optical measurements and electron spectroscopy is considered. © 1975 Springer-Verlag.