Acrylonitrile (AN) was copolymerized with N-isopropylacrylamide (NIPA) to synthesize thermosensitive bydrogels, and the on-off switch behavior of poly(NIPA-co-AN) hydrogels with different fraction of hydrophobic component (AN) was investigated. It is found that the lower critical solution temperature (LCST), the swelling ratio at certain temperature and the reswelling rate of poly(NIPA-co-AN) hydrogels decreased as AN unit fraction in copolymers increased. In order to improve the responsive rate of poly(NIPA-co-AN) hydrogels, they were further treated by surface crosslinking using N, N-methylene bisacrylamide (BIS) as a crosslinking agent. The swelling and deswelling behaviors of these copolymers were compared with those of the untreated hydrogels. The results indicated that the responsive rate of poly(NIPA-co-AN) hydrogel was improved by surface crosslinking. The resulting hydrogels bearing cyano groups with fast response have potential applications in the field of drug-controlled release and immobilization of biomolecules.