AbstractSummary: Propylene was copolymerized with 1,4‐divinylbenzene (1,4‐DVB) using rac‐Me2Si(2‐Me‐4‐Ph‐Ind)2ZrCl2 and MAO in the presence of hydrogen. 1H NMR spectra of the obtained copolymer confirmed the successful incorporation of 1,4‐DVB. 13C NMR analysis revealed a unique copolymer structure with the incorporated 1,4‐DVB units predominantly forming 1,4‐substituted phenyl repeating units in the polymer main chain. A plausible mechanism involving spontaneous insertion of terminal styryl into Zr‐H species was proposed to rationalize the unique incorporation of 1,4‐DVB.Copolymerization of propylene with 1,4‐divinylbenzene in the presence of hydrogen.imageCopolymerization of propylene with 1,4‐divinylbenzene in the presence of hydrogen.