A Au(4f) XPS spectrum has been obtained for a Au thin film deposited on a fine W wire using a 300 µm-diameter X-ray beam (MgKα, 1253.6 eV) produced by a Wolter type I mirror. The Au(4f) photoelectron count rate has also been measured as a function of beam center position when the focused beam is moved across the sample surface. This is the first microscopic XPS measurement that has been achieved using the Wolter type mirror. The observed count rate (6–7 cps) and its change across the sample surface are compared with the Au(4f) photoelectron count rates calculated in consideration of the focused X-ray beam intensity profile and the geometric configuration of the XPS measurement system. The present results suggest that XPS analysis in the micrometer range is possible with a highly brilliant X-ray source.