Disclosed is a method for formation of block copolymers using a Single Electron Transfer Living Radical Polymerization (SET-LRP) process. The process can be used to form di and tri-block copolymers from vinyl monomers. In one embodiment the SET-LRP process comprises initially forming a macroinitiator using SET-LRP to form a first block of a di or tri-block copolymer and then using SET-LRP to form additional blocks of the copolymer. The produced block copolymers have very narrow polydispersity indexes and controlled molecular weights. The process permits incorporation of photoinitiators in any of the block formation reactions. The method also includes purification processes that result in a block copolymer having very low color making it useful in a variety of applications. In one application block copolymers prepared according to the present process can be used in hot-melt adhesives.