High resolution S-1 <-- S-0 fluorescence excitation experiments on 2-vinylnaphthalene (2VN) show that the two electronic origins which appear in analogous low resolution spectra are the 0(0)(0) bands of the syn and anti conformers of 2VN. Additionally, it was found that both origins are a-axis polarized; i.e., that the S-1 <-- S-0 optical transition moments are parallel to the long axes of both conformers. This information, together with the measured rotational constants, partial vibrational analyses of the low resolution spectra, and the results of ab initio calculations, strongly suggests that the S-1 <-- S-0 transition is "polyene-like"; i.e., that significant bond-order reversal accompanies the absorption of the photon. This view is supported by the approximate vinyl torsional potential energy surfaces of both s- and a-2VN that have been derived from the data.