We present the S1 picosecond transient Raman spectra of trans-4,4‘-diphenylstilbene (DPS) obtained at excitation wavelengths of 287 and 310 nm and probe wavelengths of 630 and 660 nm. We compare spectra at different pump and probe wavelengths in order to evaluate the role of conformational dynamics and vibrational relaxation in S1 DPS. In this study, we find that dioxane and methylene chloride accept excess vibrational energy from the photoexcited solute in a different manner. We attribute this variation either to a difference in the local solvent structure or to the difference in the density of states between methylene chloride and dioxane. We also find that the relative intensities of certain bands demonstrate a dependence upon the pump and probe wavelengths. From these data, we have established that the change in relative intensity with delay is a marker for the dynamical shift in the S1 potential energy surface. The dependence of this dynamical change on excitation wavelength demonstrates that we are examining a “nonstationary” state that evolves on a 10−50 ps time scale.