Resonance Raman spectra of poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl-C61-butyric acid methyl ester blend thin films display progressions of overtone and combination bands (up to two harmonics) involving the dominant symmetric C=C backbone stretching mode of P3HT that encode excited state vibrational displacements and dynamics information. Contributions from both crystalline (aggregated) and amorphous (unaggregated) P3HT domains are resolved and intensities are analyzed using the time-dependent theory of spectroscopy. Raman spectra, excitation profiles, and absorption spectra are simulated with the same parameters using a single electronic state description for each P3HT form. Time-dependent wavepacket overlaps expose vibrational coherence on sub-100 fs timescales, which is usually difficult to extract from conventional ultrafast pump-probe spectra and transients of polymer∕fullerene blends. The results demonstrate the potential of simpler CW resonance Raman approaches to uncover excited state geometry changes and early vibrational dynamics from distinct morphological forms in polymer∕fullerene blends.