Linear and star-shaped poly( epsilon -caprolactone) (PCL) block copolymers containing poly(meth)acrylate segments with glycidyl, 2-(trimethylsilyloxy)ethyl and tert-butyl pendant groups were synthesized using mono-, di- and trifunctional PCL macroinitiators and appropriate (meth)acrylate monomers by controlled radical polymerization. The well-defined structures with narrow molecular weight distributions indicate the coexistence of semi-crystalline PCL and amorphous poly(meth)acrylic phases. The hydrophobic nature of the block copolymers can be easily converted to amphiphilic, which with biodegradable and biocompatible PCL segments are promising as polymeric carriers in drug delivery systems. copyright 2012 Society of Chemical Industry Linear and star poly( epsilon -caprolactone) (PCL) block copolymers containing poly(meth)acrylate segments with glycidyl, 2-(trimethylsilyloxy)ethyl and tert-butyl groups were synthesized. The copolymers with biodegradable and biocompatible PCL segments are promising as polymeric carriers in drug delivery systems.