We use photoemission spectroscopy to study electronic structures of pristine and K-doped solid picene. The valence band spectrum of pristine picene consists of three main features with no state at the Fermi level (E(F)) while that of K-doped picene has three structures similar to those of pristine picene with new states near E(F), consistent with the semiconductor-metal transition. The K-induced change cannot be explained with a simple rigid-band model of pristine picene but can be interpreted by molecular-orbital calculations considering electron-intramolecular-vibration interaction. Excellent agreement of the K-doped spectrum with the calculations points to importance of electron-intramolecular-vibration interaction in K-doped picene.