The laser-induced fluorescence (LIF) spectra, both the fluorescence excitation spectra (FES) and single vibrational level fluorescence spectra (SVLF) from several different vibronic states, along with the ultraviolet (UV) absorption spectra of 1,4-benzodioxan have been recorded and analyzed. A detailed energy map has been constructed for four low-frequency vibrations and their combinations for both the S-0 and S-1(pi, pi*) electronic states. These are v(48) (ring-bending), nu(25) (ring-twisting), nu(47) (ring-flapping), and v(24) (skeletal-twisting). Both the experimental and ab initio calculations show the molecule to be twisted in both the S-0 and S-1(pi,pi*) states with high barriers to planarity. The experimentally determined ring-twisting quantum states, which are confined to the lower regions of the potential energy surface, were used to calculate one-dimensional potential functions in terms of the twisting coordinates, and the extrapolated barriers were estimated to be 5700 and 4200 cm(-1) for the S-0 and S-1 states, respectively. Two-dimensional calculations, which included the interactions with the bending modes, gave values of 3906 and 1744 cm(-1), respectively. The S-0 value compares favorably with the ab initio value of 4095 cm(-1).