A synchrotron-based photoionization spectrum of azulene shows a significant additional vibrational fine structure when compared to previous studies. This spectrum was successfully analyzed by using Franck-Condon (FC) methods. Previously reported zero-kinetic-energy electron spectra for azulene have been reinterpreted in FC terms, leading to some alternative assignments to the earlier work. The sequence of ionic states has been determined by using ab initio configuration interaction (CI) methods, leading to reliable theoretical values for both the calculated adiabatic ionization energy (AIE) and vertical ionization energy (VIE). VIEs were calculated by both symmetry-adapted cluster (SAC-CI), together with Green's function (GF) and Tamm-Dancoff approximation (TDA), and single excitation CI methods; AIEs for highest states of each symmetry were determined by open-shell self-consistent field (SCF) methods at the restricted Hartree-Fock level. Complete active space SCF was used for the pairs of 12A2 + 22A2 and 12B1 + 22B1 states, each of which occurs as antisymmetric and symmetric (higher energy) combinations. The combined ionic state sequences (AIE and VIE) from these methods are 12A2 < 12B1 < 22A2 < 22B1. The photoelectron spectrum (PES) shows a series of broadbands above 11 eV, each of which is attributed to more than one ionization. The calculated PES sequence of states of up to 19 eV shows that the SAC-CI and GF results are in almost exact agreement. The internal spacing of the bands is best reproduced by the simpler GF and TDA methods. States involving simultaneous ionization and electronic excitation are considered by both SAC-CI and TDA methods.