Environmentally sensitive hydrogels (ESH) with inter-complex and amphoteric properties were prepared by thermal free radical polymerization of vinylpyrrolidone (VP), methacrylic acid (MA), and N,N'-methylene bisacrylamide. Spectroscopic and thermal characterizations of ESHs were performed using FTIR and TGA. To determine the effects of ESHs on swelling properties, swelling and diffusion studies were performed at different pHs, temperatures, and salt solutions. While the inter-complex formation between VP and MA was monitored with UV, the amphoteric property and environmental sensitivity of VP/MA-H were determined by swelling studies. In the binding of Cu(II) ion binding onto VP/MA-H experiments, a Langmuir type (L) adsorption was observed concerning the Giles classification system. Binding parameters such as equilibrium constant (KL), monolayer coverage (Qm), and maximum fractional occupancy (FO%) were calculated as 0.16 L gESH−1, 30 MgCu(II) gESH−1, and 81%, respectively. In the light of these findings, it can be said that strong electrostatic interactions between the anionic groups in the VP/MA-H and Cu (II) cations are more effective in the interaction of the heavy metal ions with the hydrogel. The outputs of this study are important in the preparation of effective vinylpyrrolidone/methacrylic acid for hydrogel applications in electrostatic interactions, adsorption, and removal of organic toxic wastes.