Surface relief gratings (SRGs) recorded on Langmuir-Blodgett (LB) films of an azobenzene homopolymer were visualized using micro-Raman imaging. Raman scattering (RS) was achieved using the 780 nm laser line while pre-resonance Raman scattering (pre-RRS) and resonance Raman scattering were achieved using the 633 and 514.5 nm laser lines, respectively, Pre-surface-enhanced resonance Raman scattering (pre-SERRS) and surface-enhanced resonance Raman scattering (SERRS) were collected for the LB films covered with a 6 nm thick silver island film. The SRG could be chemically identified by the spatial variation in the Raman signal scattered by the film due to a concentration gradient. The pre-SERRS provided signals of the same intensity along and across the grooves, indicating that the molecular architecture at the SRG surface is the same at the peaks as in the valleys.