Polyisoprene (PI) was pre-polymerized by using benzyl diethyldithiocarbamate (BDC) as an iniferter. The obtained PI was subsequently used to react with methyl methacrylate (MMA) in order to investigate whether the relevant block copolymers can be achieved. Results from H-1-NMR and GPC reveal that the PI-PMMA block copolymers were formed. This suggests that polymerization of isoprene through the use of BDC proceeded via a (psuedo) "living" mechanism.