Diblock copolymers of poly(methylene-b-epsilon-caprolactone) (PM-b-PCL) were synthesized in two steps: (a) polyhomologation, to obtain, following oxidative cleavage of the carbon boron (PM, block,), an alpha-hydroxyl-omega-methyl polymethylene (PMOH, CH3 [CH2](m) OH) and, following the transfer reaction to the ring-opening polymerization catalyst, (b) ring-opening polymerization (ROP) of epsilon-caprolactone (CL) (PCL, block(2)). In addition, a series of homopolymers derived from poly(epsilon-caprolactone) (PCL) oligoesters containing an end group of docosyl (CH3-[CH2](21)- or C-22; C-22-PCL) were obtained as a model to compare their physical properties by DSC with those of PM-b-PCL. The oligomers derived from PM-b-PCL and C-22-PCL were characterized by H-1 and C-13 NMR, AFM, DSC, GPC, and MALDI-TOF. PM-b-PCL and C-22-PCL were evaluated as compatibilizers for PE/PCL polymer blends. Identification and analysis of optimized blocks of PM-b-PCL by POM showed improved mixing of PE/PCL blends.