Three dinuclear metal complexes (comprised of six-coordinated nNi2L and five-coordinated nCu2L and nZn2L) were confirmed by means of elemental analysis, UV-vis and IR spectra, and single X-ray crystal structural analysis in a spectroscopic study. The stable structures of these nNi2L, nCu2L, and nZn2L complexes in poly(vinylalcohol) (PVA) films were analyzed using UV-vis spectra. The molecular orientation of hybrid PVA film materials after linearly polarized light irradiation was analyzed to obtain the polarized spectra and dichroic ratio. Among the three materials, nNi2L and nZn2L complexes indicated an increasing optical anisotropy that depended on the flexibility of the complexes. We have included a discussion on the formation of the pseudo-crystallographic symmetry of the components in a soft matter (PVA films).