The valence bands of polypyrrole doped with various types of dopants have been investigated in order to clarify the polymer configurations associated with lattice distortion due to the dopants. Ultraviolet photoemission spectroscopy (UPS) spectra of doped, intermediate doped and reduced polypyrrole exhibits two characteristic shoulders theoretically assigned to 2b(1) and 1a(2) pi-orbitals. A decrease of the density of states (DOS) at the 2b(1) level and an increase of the DOS at 1a(2) are observed in the reduced state. UPS spectra of polypyrrole doped with (p)-toluenesulfonate, which has a pi-orbital, shows large energy shifts of the main and shoulder peaks are observed. The results indicate that doping could affect the 2b(1) valence band related to the pi-orbitals of N atom, which suggests the lattice distorted structure of the conjugated polymer system.