This work is devoted to the design of a novel family of hydrosoluble biomaterials: poly(N-vinyl-2-pyrrolidone) (PVP)-based graft copolymers. A synthesis route has been elaborated in which omega-functionalized PVP is prepared via chain-transfer radical polymerization, end-group modified, and subsequently grafted onto a polyhydroxylated backbone, typically dextran or poly(vinyl alcohol). The resulting graft copolymer biomaterials are designed for use in various biomedical applications, particularly as materials with a stronger potential for plasma expansion than already existing products have. The graft copolymers are potentially degradable because the PVP grafts are connected to the polyol backbone via a hydrolytically labile carbonate or ester linkage. The degradation of the graft copolymers was performed in vitro over a period of 6 weeks.