Photoion and photoelectron yields were measured for poly(methylmethacrylate) in the photon energy region of 8–40 eV using synchrotron radiation. Further, the valence‐band structure was investigated with ultraviolet photoelectron spectra and valence effective Hamiltonian calculations. A significant difference was observed between the photon energy dependencies of photoion and photoelectron yields. The threshold energy for photoion emission was found to be 10.5 eV, while that for photoelectron emission was 8.5 eV, indicating holes created near the valence‐band top do not contribute to the ion emission. At the higher‐energy region, the ion emission efficiency was found to be enhanced in the photon energy region of 17–28 eV. The difference between the threshold energies of photoion and photoelectron emission and the enhancement of the photoion emission are discussed in conjunction with the valence‐band structure.