Kelvin probe force microscopy allows to determine not only the surface topography as does atomic force microscopy, but in addition also delivers images of the surface work function on a nanometer scale. Operation in ultrahigh vacuum improves the lateral and energy resolution and allows to obtain absolute work function values. In this paper we will introduce the method and give examples for the application to solar cell materials and devices. We review examples where the surface of an oriented CuGaSe2 film showed distinct work function values for differently oriented facets of single grains, with differences as high as 250 meV, possibly affecting the power conversion efficiency of a solar cell. A cross-sectional study of a complete solar cell device based on the CuGaSe2 absorber material revealed the formation of an additional MoSex layer between the Mo back contact and the absorber. We will present results of measurements at individual grain boundaries of the absorber material. Furthermore, band bending effects at these grain boundaries are discussed and compared to results from transport studies. (C) 2003 Elsevier Science B.V. All rights reserved.