The binary copolymerization of maleic anhydride (MA) and N-vinyl caprolactam (VCL) or considered as acceptor (A)-donor (D) monomer systems were used (MA:VCL) 50:50 in BPO (0.5%) as an initiator at 70 degrees C under nitrogen atmosphere. The functional copolymers, having a combination of rigid/flexible linkages and an ability of complex-formation with interlayered surface of organo-silicate, and their nanocomposites have been synthesized. Interlamellar in situ complex-radical copolymerization of intercalated monomer complexes of MA and VCL undergoes with stearyl amine surface modified montmorillonite (O-MMT) and monomer mixtures. Charge transfer complex formation was followed and identified by UV-Vis-NIR spectroscopy. Equilibrium constant (K-AD) molar absorption coefficient (E-AD)) of the complex were determined by the Benesi-Hildebrand, Scott and Ketaalar equations respectively. The results show that copolymerization of MA:VCL system was preceded via alternating copolymerization mechanism. Obtained functional alternating copolymer and copolymer/O-MMT nanostructures were characterized by XRD and TEM.