We report the analytical expressions of the two-dimensional potential energy surfaces (PES) spanned by the puckering and flapping vibrations in the So and S, states of 1,3-benzodioxole (BDO). Both PES are obtained from S-0 and S-1 energies computed on a grid of 2500 molecular geometries at the CASPT2 level. Both the So and S-1 PES are anharmonic, and the planar geometry corresponds to a barrier that separates two minima at nonplanar geometries along the puckering/flapping deformations. Eigenvalues and eigenvectors of the mixed puckering/flapping modes are calculated by the Meyer flexible model. Improved vibronic levels, in better agreement with the observed spectra, are obtained by suitably optimized CASPT2 surfaces. To assign the lower-energy (0-500 cm(-1)) portion of emission and absorption spectra, we evaluate the band intensities by estimating the Franck-Condon factors between the puckering/flapping eigenvectors of the S-0 and S-1 states. From these calculations, we obtain a satisfactory assignment of the ground state IR spectra and of the fluorescence excitation spectrum. Both assignments are supported by the analysis of the vibrational structures of several single vibronic level (SVL) fluorescence spectra. The successful interpretation of these spectra shows that the S-0 and S-1 PES that we derive for BDO are substantially correct. The barrier heights in the two states are similar: 125.7 and 190.4 cm(-1) in S-0 and in S-1, respectively. In S-0, the barrier is associated essentially with the puckering motion. In S-1, it involves to a considerable extent also the flapping coordinate, whose vibrational frequency is much lower in S-1 than in S-0. This fact introduces a substantial Duschinsky effect in the S-0-S-1 transitions of BDO.