A novel pH-sensitive graft copolymer (PVAM-g-CSt) was synthesized from maleated poly(vinyl alcohol) (PVAM) and cassava starch (CSt) through a grafting reaction using potassium persulfate as a thermal initiator. The chemical structure of the PVAM-g-CSt was revealed by FTIR and ether linkage of the graft copolymer was observed at 1089 cm−1. The degree of grafting of the copolymer was found to range between 40 and 82%, depending on the PVAM/CSt ratio. The highest tensile strength was found at a ratio of 9:1 PVAM/CSt. In addition, the swelling ratio in water increased with increasing proportions of CSt in the PVAM-g-CSt due to the decrease in the degree of grafting. The resulting hydrogel exhibits good pH sensitivity in different pH mediums. The graft copolymer easily degraded in natural soil, especially at high proportions of CSt in the blend.