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The electronic structure and the geometric arrangement of picene molecules adsorbed on Ag(111) were studied by means of photoemission and near-edge X-ray absorption fine-structure spectroscopies (NEXAFS). While the valence band of a picene monolayer shows a clear metallic state that evolves with alkali metal doping, in the case of a picene multilayer there is no evidence of metallic states evolving with doping. Our data suggest that the bulk ultrahigh-vacuum films of Kxpicene are in an insulating phase, and we attribute this behavior to a strong electron–electron Coulomb interaction that is instead screened in the monolayer. The NEXAFS profiles of different picene layers show a coverage-dependent orientation, from flat molecules (monolayer) to an orientation of ∼40° of the molecular long axis with respect to the substrate surface (multilayer). The observed molecular orientations are in disagreement with the expected crystal structure of the bulk material and may explain the presence of insulating states in strongly correlated doped picene multilayers.