Spectroscopic characterization and fabrication of Langmuir and Langmuir-Blodgett (LB) films of an azopolymer-pyridine (PAzPy) are reported. UV-visible absorption and fluorescence spectra, Fourier transform infrared (FTIR) spectra, and Raman spectra were recorded. The vibrational assignment of the observed spectra is supported by a complete geometry optimization, followed by vibrational frequency and intensity computations of both the trans and cis forms of the monomer (AzPy) using density functional theory at the B3LYP 6-31G(d,p) level of theory. Langmuir monolayers of the polymer (PAzPy) were formed at the water-air interface, and LB films of high quality were formed onto solid substrates. The polymer LB films were investigated by surface-enhanced Raman scattering.