Polymer sponges with molecular recognition provide a facile approach to water purification and industrial separation with easy operation. Herein, a thiolated polyethyleneimine (PEI)-based polymer sponge was prepared through cryo-polymerization of PEI, followed by grafting of PEI and then post-modification of the amine functionalities present within the hyperbranched structure with methyl mercaptoacetate, which afford high density of thiol functional groups on the surface of the sponge. The developed sponge was characterized by scanning electron microscopy and element analysis, and the adsorption kinetic and isotherm studies were conducted in detail. The sponge presents a remarkable maximum adsorption capacity of 2899.7 mg/g, which can be attributed to its high density of thiol functionalities. The sponge also shows excellent selectivity toward Hg against other metal ions and natural organic matter, indicating its great potential in removing mercury from real water bodies. In addition, the sponge can be chemically regenerated and exhibits good reusability, which decreases the economic and environmental impacts. Hence, the high removal efficiency, high selectivity toward mercury, and good reusability of the sponge material highlight it as a promising sorbent for mercury removal in water pollution treatment.