Fluorescence spectra of trans-l-(2-naphthyl)-2-phenylethene (NPE) obtained under varying conditions of excitation wavelength and oxygen concentration in methylcyclohexane are resolved into two distinct components by application of principal component analysis with self-modeling. The key to obtaining unique spectral solutions in the constraint is that Stern-Volmer quenching plots for the individual conformers be independent of excitation wavelength. Resolved conformer fluorescence-excitation spectra are obtained by application of principal component analysis on a matrix of fluorescence-excitation spectra. Consistency between pure component fluorescence and fluorescence excitation spectra is established by use of a two-dimensional fluorescence excitation-emission matrix. Fluorescence quantum yields and the pure component fluorescence-excitation spectra are employed to resolve the UV absorption spectrum of NPE into pure component conformer absorption spectra. The results are compared with those from earlier studies based on the analysis of fluorescence decay data.