The S-2(pi pi*)<--S-0 spectrum of jet-cooled benzaldehyde has been recorded by laser ionization. The O-0(0) band has been located at 35 191 cm(-1). Ten fundamental vibrations have been assigned following a vibrational analysis assisted by theoretical calculations. Ab initio molecular orbital methods have been used to examine the electronically excited states of benzaldehyde. On pi*<--pi excitation the primary geometric distortions are in the formyl group, while on pi*<--pi excitation these are mainly in the aromatic ring. Vibrational frequencies were found to be in reasonable agreement with the experimental data for the states studied (S-0, S-1(n pi*), S-2(pi pi*), and T(n pi*)), and the calculations provided a useful guide in assigning the observed excited state fundamentals.