A synthetic method with broad spectrum of application in the preparation of self-organizing amphiphilic copolymers having poly(glycerol monomethacrylate) (PG2MA) as a hydrophilic part is herein reported. The approach relies on the facile preparation of silylated glycerol monomethacrylate (G2MA-TMS) monomer, and its controlled atom transfer radical polymerization (ATRP) in organic media, which produced well-defined (co)polymers with predictable molar mass and low dispersity, followed by desilylation. The wide scope of such a strategy was demonstrated by the successful synthesis of original polycaprolactone-b-poly(glycerol monomethacrylate) (PCL-b-PG2MA) diblock copolymers with the ability to self-assemble into ordered structures (micelles and vesicles) in an aqueous medium.