By comparison of the E.S.C.A. valence band spectra recorded in the solid phase for polyacenes (benzene, naphthalene, anthracene, and tetracene) with gas phase results, important energy parameters (energy gap, work function) of these compounds have been obtained. The trends observed in the evolution of the main C1sshake-up positions and intensities serve to assign the π satellites to transitions of the type nb1→b1*.