Bis-boron-thexyl-silaboracycle was prepared by hydroboration of 1,4-bis(methyldivinylsilyl)butane with thexylborane and used to initiate the polyhomologation of dimethylsulfoxonium methylide to afford well-defined hydroxy-terminated 4-arm polyethylene (PE) stars. The synthesized PE stars were transformed to (PE-b-PCL)4 starblock copolymers via the ring-opening polymerization of ϵ-caprolactone (CL) initiated by the hydroxyl end groups of (PE-OH)4 in the presence of P2-tBu phosphazene base. Esterification of the hydroxyl groups of the OH-terminated PE star with 2,2-dichloroacetyl chloride led to (PE-Cl2)4 which was used as initiator (eight initiating atom transfer radical polymerization, ATRP, sites) for the synthesis of (PE-b-PMMA2)4 dendrimer-like stars by the ATRP of methyl methacrylate (MMA). All intermediates and final products were characterized by high temperature gel permeation chromatography and proton nuclear magnetic resonance spectroscopy. © 2016 The Royal Society of Chemistry.