The vibronic structure of the S-1 <-> S-0 electronic transition of jet-cooled cis-2-methoxynaphthalene (2MXN) has been investigated in detail by use of laser-induced excitation and emission spectroscopy. Fluorescence hole-burning experiments were employed to establish vibronic excitations due to the presence of the cis isomer. Eighteen ground state and 15 excited state vibrational frequencies were assigned by analyses of 25 single vibronic level fluorescence (SVLF) spectra, including the methoxy and methyl torsional mode frequencies. Strong vibrational state mixing in S-1 was observed in several SVLF spectra at low vibrational excess energies, attributed to the combined appearance of Fermi resonances and Duschinsky rotation. Vibrational assignments of S-0 frequencies were supported by ab initio calculations, employing the RHF/6-31G** method. Optimization of ground state geometries revealed that the cis isomer is the lowest energetic ground state conformer of 2MXN, in agreement with experiment. Furthermore, excited state ab initio calculations using the CIS/6-31G** method predicted that the first excited state of cis-2MXN correlates with the S-2 state of parent naphthalene, exhibiting a short-axis-oriented transition dipole moment.