Two-photon polarized fluorescence excitation and vibronically resolved one-photon dispersed fluorescence spectra of the long-wavelength absorbing van der Waals complexes of indole with water, methanol, and formamide were examined for the purpose of firmly assigning the nature of the lowest singlet excited electronic state. The two-photon spectra for all of these complexes have circular/linear polarization ratios of absorptivity (Omega-values) that show that excitation is to the L-1(b) state. Analysis of the Franck-Condon (FC) patterns of the dispersed fluorescence for these indole-polar solvent complexes show that emission is also from the L-1(b) State in each case. In the emission spectra, the intensity ratios of the origin and v(26) lines are about 2:1, which is the value expected for L-1(b) emission. The v(26) vibration is the most intense nonorigin vibronic line, as expected for L-1(b) emission. Finally, there is little or no intensity from the v(8), y(9), and v(10) vibrations, which would be strongly active with emission from the L-1(a) state. These results show unequivocally that for these indole-polar solvent complexes the L-1(a) state does not shift in energy below the L-1(b) state-contrary to the interpretation of several recent papers. Further support is given to the assignment of L-1(b) emission by spectral simulations. The jet-cooled complexes do not exhibit excited state complex (exciplex) characteristics, wherein the solvent is much more strongly bound in the excited state than in the ground state.