Accurate measurement of work function is essential in many areas of research and development. Despite the importance of photoelectron spectroscopy as a technique for measuring work function, there has been relatively little discussion in the literature of how to conduct accurate measurements. We review the basic technique of measuring work function using ultraviolet photoelectron spectroscopy and discuss several common sources of error related to the experimental setup. In particular, the sample-detector geometry is found to be a key experimental parameter; accurate results are only obtained when the sample is perpendicular to the electron detector. In addition, we demonstrate that photoelectron work function values correspond to the minimum work function "patch'' on a non-uniform surface, in contrast to the average work function measured by other techniques, such as the Kelvin probe method. (C) 2009 Elsevier B.V. All rights reserved.