Langmuir-Blodgett (LB) monolayers of magnesium and palladium tetra-tert-butylphthalocyanine complexes (MPc(t), M = Mg, Pd) have been prepared on various substrates. The formation of stable Langmuir layers and the surface pressure versus molecular area isotherms are reported for these nonamphiphilic molecules. A detailed spectroscopic characterization of MPc(t) materials and LB layers is given using spontaneous Raman scattering (RS), resonance Raman scattering (RRS), surface-enhanced resonance Raman scattering (SERRS), transmission and reflection-absorption FT-IR spectroscopy (RAIRS), and UV-visible spectroscopy. The orientation of MPc(t) monomolecular films transferred to smooth gold films and ZnS substrate was probed by RAIRS and transmission FT-IR spectroscopy, respectively. The effect of the adsorption of NO2/N2O4, SO2, and NH3 gases on LB films of MPc(t) materials was monitored in the visible spectrum.