Hydrogel has been widely used in reservoir regulation for enhancing oil recovery, however, this process can experience negative influences on the properties and effects of the hydrogels. Therefore, developing novel hydrogels with excellent environmental responsiveness would improve the formation adaptability of hydrogels. In this study, novel polyvinyl polyamine hydrogels were synthesized by a ring-opening addition reaction between polyvinyl polyamines and polyethylene glycol glycidyl ether. The results of atomic force microscopy and transmission electron microscopy showed that the polyvinyl polyamine gel had a porous and irregular bulk structure and was endowed with water storage. With the temperature rising from 30 °C to 60 °C, the transmittance of diethylenetriamine hydrogel decreased from 84.3% to 18.8%, indicating that a phase transition had occurred. After the polyvinyl polyamine hydrogel with low initial viscosity was injected into the formation in the liquid phase, the increase of the reservoir temperature caused it to turn into an elastomer, thereby migrating to the depth of the reservoir and achieving effective plugging. Polyvinyl polyamine hydrogel could improve the profile of heterogeneous layers significantly by forcing subsequent fluids into the low permeability zone in the form of elastomers in the medium temperature reservoirs of 40–60 °C. The novel environmentally responsive polyvinyl polyamine hydrogels, capable of phase transformation with temperature, exhibited superior performance in recovering residual oil, which was beneficial for applications in reservoir profile control and oilfield development.