Herein, the PCL‐PEG‐PCL macro xanthate reversible addition−fragmentation chain‐transfer agent was obtained on the polyethylene glycol (PEG) (600, 1000, and 1500 g/mol) block, after the addition of ɛ‐caprolactone via ring‐opening polymerization. Then, Poly (Styrene‐b‐ԑ‐Caprolactone‐b‐PEG‐b‐ԑ‐Caprolactone‐b‐Styrene) pentablock copolymer was synthesized RAFT solution polymerization technique via mediated PCL‐PEG‐PCL xanthate macro‐RAFT agents and 2,2′‐azobisisobutyronitrile as initiator. The products were demonstrated using Fourier transform infrared spectrophotometer (FT‐IR), proton nuclear magnetic resonance (1H‐NMR), carbon nuclear magnetic resonance (13C‐NMR), differential scanning calorimetry (DSC), and gel permeation chromatography (GPC) analyses. First‐order linear kinetic graphs of the reaction mechanism were observed with an increase in molecular weights (MW) between 16 000 and 36 000 g/mol. The narrow dispersity (Đ = 1.40 – 1.48) polymer formation of styrene (St) controlled by RAFT polymerization confirms the increase in molecular weight according to the polymerization time. The reaction kinetics were first order and the rate constants were found to be k1 = 6.16 × 10−4s−1, k2 = 6.91 × 10−4s−1 and k3 = 7.33 × 10−4s−1. Thermal and spectroscopic analyzes prove that the reactions were carried out successfully.This article is protected by copyright. All rights reserved