We have done Raman and luminescence measurements on a variety of PPV derivatives and oriented polymer blends. Changes in the observed Raman spectra for the polymers studied are consistent with molecular level changes in the polymer structure. Low frequency modes, which may be torsional modes of the polymer, have been observed for the first time. By comparison to site-selective luminescence spectra, it is found that at least two different phonons contribute to the vibrationally resolved luminescence spectra.