We report detailed studies of local electronic properties in nanostructured thin metallic films using scanning photoionization microscopy. This novel form of microscopy combines the advantages of diffraction-limited optical excitation with the ability to detect both photons and low kinetic energy photoelectrons, permitting sensitive characterization of heterogeneous surfaces under vacuum conditions. Using this technique, correlated measurements of multiphoton photoemission cross section and optical penetration depth are reported for Au films supported on Pt. These results present a first step toward combining confocal fluorescence or Raman microscopy with time-resolved photoelectron imaging spectroscopy in complex metal film environments, which should be ideally suited to investigating local plasmonic effects in nanostructures.