Methods for synthesizing a random copolymer having a phosphorylcholine group. Syntheses involving a reaction mixture containing a chain transfer agent (CTA), a solvent, a hydrophobic methacrylate monomer, a 2-methacryloyloxyethyl phosphorylcholine (MPC) monomer, and, optionally, an initiator. The random copolymers produced by such synthesis methods having a polydispersity index (PDI) of less than about 1.3 and a peak molecular weight (Mp) of less than about 130,000. Polymer blends and medical devices including such random copolymers, and methods of treating a mammal using such random copolymers or medical devices.