Thin films of hybrid inorganic:organic composites [TiO2:copper phthalocyanine, Al2O3:6-propionyl-2-(dimethylamino)naphthalene, and Al2O3:rhodamine 6G] were fabricated by mixing the constituents in the gas phase via the technique of laser-assisted molecular beam deposition. These films were characterized by UV-visible, infrared, and steady-state fluorescence spectroscopic techniques. UV-visible and infrared spectra of TiO2:copper phthalocyanine films indicate that the organometallic compound, copper phthalocyanine, is trapped within the host TiO2 matrix without degradation. The local microenvironment of the organic components in these composite films were studied by steady state fluorescence spectroscopy. Emission spectra indicate that the organic dye molecule, rhodamine 6G, is trapped within the Al2O3 matrix as the monomer without aggregation. The spectral red shift of the emission peak and the full width at the half maximum suggest the environmentally sensitive probe, 6-propionyl-2-(dimethylamino) naphthalene, molecules are embedded within the Al2O3 matrix as opposed to being adsorbed on the Al2O3 surface.