Syntheses, structural characterizations, photoluminescence, and adsorption properties of three new azo-functionalized Cd(II)-MOFs, namely, {[Cd(azbpy)(msuc)]center dot 2.5(H2O)}(n) (2), {[Cd(azbpy)(mglu)]center dot 5(H2O)}(n) (3), and {[Cd-1.5(azbpy)(2)(glu)]center dot(NO3)center dot MeOH}(n) (4) [where msuc(2-) = methylsuccinate; mglut(2-) = methylglutarate; glut(2-) = glutarate; azbpy = 4,4'-azobispyridine] have been reported. The compounds show different structures only with the variation of aliphatic dicarboxylates. The photoswitching behavior for the above-mentioned newly synthesized Cd(II)-MOFs along with one of our previously reported other azo-functionalized Cd(II)-MOF, namely, {[Cd(azbpy)(suc)]center dot 2(H2O)}(n) (1), has been studied extensively. At photoilluminated condition, the conductivity values can draw a clear structure-property relationship among the structures of compounds 1-4. Single crystal structural analysis reveals that all the compounds exhibit a three-dimensional (3D) framework connected by azbpy linker and respective aliphatic dicarboxylate through their bis-chelating mono/bis oxo-bridging fashion. Compounds 1-3 exhibit an iso-structural honeycomb like 3D framework showing the same coordination environments, where the metal-carboxylate 2D sheets of compounds 1-3 are pillared by N,N'-donor azbpy linkers. On the other hand, compound 4 exhibits a 2-fold interpenetrated 3D framework with a little difference in its coordination environment and the pillaring of 1D metal-carboxylate ladder by azbpy linkers. All the compounds significantly demonstrate their enhanced sensitivity under light rather than the dark condition. The gas and solvent vapor sorption studies have been performed for the synthesized compounds 2-4. Moreover, compound 2 exhibits an enhanced type IV selective CO2 adsorption isotherm over N-2 along with the appearance of gate opening phenomena in that.