Rotationally resolved electronic spectra of several low frequency vibrational bands that appear in the S1 <- S-0 transition of 4-fluorobenzyl alcohol (4FBA) in the collision-free environment of a molecular beam have been observed and assigned. Each transition is split into two or more components by the tunneling motion of the attached -CH2OH group. A similar splitting is observed in the microwave spectrum of 4FBA. Analyses of these data show that 4FBA has a gauche structure in both electronic states, but that the ground state C1C2-C7O dihedral angle of similar to 60 degrees changes by similar to 30 degrees when the photon is absorbed. The barriers to the torsional motion of the attached -CH2OH group are also quite different in the two electronic states; V-2 similar to 300 cm(-1) high and similar to 60 degrees wide in the So state, and V-2 similar to 300 cm(-1) high and similar to 120 degrees wide (or V-2 similar to 1200 cm(-1) high and similar to 60 degrees wide) in the S-1 state. Possible reasons for these behaviors are discussed.