Using nanoESCA, a novel energy-filtered PEEM instrument equipped with an aberration corrected energy filter, we have imaged micro-sized (1 μm) polished copper grains with UV (4.9 eV) and VUV (21.1 eV) radiation. Energy-filtered UV-PEEM images allow to reach a lateral resolution of 40 nm. From series of energy?filtered images, reconstructed VUV microspectra taken over typical areas of 600 nm², directly show up variations in the local work function, on an absolute energy scale, of grains having different crystalline orientation. Work function values measured from fitting of the photoemission threshold are consistent with < 111 >, < 100 > or < 110 > crystalline orientations (work function of 4.9, 4.6, and 4.5 eV, respectively). This experiment opens new possibilities in the local characterization of surfaces in the sub-micron range with high energy- and lateral resolutions. [DOI: 10.1380/ejssnt.2006.431]