Photoelectron spectra of 1,3-cyclohexadiene (CHD) have been obtained by three-photon, double resonance ionization via the ultrashort lived B-1(2) (S-2) state, and a previously unknown superexcited valence state at 9.0-9.5 eV. Upon two-photon excitation to the superexcited state there is an ultrafast internal conversion leading to a set of vibrationally excited Rydberg states. Ionization out of these latter states by a third photon results in photoelectron spectra that show two prominent Rydberg series with quantum defects of delta = 0.58 +/-0.04 and 6 = 0.98 +/-0.02, respectively.