A novel pH-temperature-sensitive elastomer was made from maleate poly(vinyl alcohol)-graft-isopropylacrylamide (PVAM-graft-PNIPAM), namely PVNI and deproteinized natural rubber (DPNR) in a water-based system. The swelling ratio in water of PVNI/DPNR hydrogel enhanced as a function of PVNI portion in hydrogel due to increasing of hydrophilic group in the hydrogel. Surprisingly, the percentage of swelling in water of PVNI/DPNR hydrogel 7:3 is 24 times based on pristine DPNR. In addition, the highest tensile strength of PVNI/DPNR hydrogel was found at 7:3 PVNI/DPNR. The highest elongation at break of PVNI/DPNR hydrogel was improved after the addition of DPNR. Moreover, the resulting smart hydrogel showed a good pH-temperature sensitivity. In addition, it yielded a good polymer membrane for encapsulating capsaicin (CSC) in different media. After its use, it also easily decomposed in the natural environment.