Grafting-from (GF) is an important yet underdeveloped strategy toward protein polymer conjugates. Here, we report a simple cryopolymerization method that enables highly efficient GF synthesis of cell-penetrating protein-polydisulfide conjugates. Rapid and controlled ring-opening polymerization of 1,2-dithiolanes under cryo-conditions can be initiated by proteins bearing a reactive cysteine, owing to both favored thermodynamics and augmented kinetics arising from frozen-induced high local concentration of substrates. This method is applicable to various wild-type or genetically engineered proteins without the need of chemical installation of an initiation group. The resulting conjugates can be reversibly degrafted under mild conditions to regenerate functional "native" proteins in a traceless fashion. These unique features make such conjugates highly useful in applications such as a dynamic switch of protein functions, cytosolic delivery of protein therapeutics, and protein purification. The method is also potentially useful for the in situ growth of other types of polymers from protein surface.