Improved processes for atom (or group) transfer radical polymerization (ATRP) and novel polymers have been developed and are described. In certain embodiments, novel copolymers comprising a least one polymeric branch or polymeric block with a predominantly alternating monomer sequence are described. Novel copolymers comprising a least one polymeric branch or polymeric block with a gradient monomer structure are described. Additionally, novel copolymers comprising a least one polymeric branch or polymeric block with a predominantly periodic monomer sequence are also described. Novel copolymers having a water soluble backbone and at least two hydrophobic polymeric branches grafted to the water soluble backbone are also described.