In this contribution, we reported the synthesis of a series of POSS-terminated polycyclooctadiene (PCOD) telechelics via ring-opening metathesis polymerization (ROMP) approach. Toward this end, 1,4-diPOSS-but-2-ene was synthesized via copper-catalyzed Huisgen cycloaddition reaction (i.e., click chemistry); it was then used as a chain transfer agent (CTA) for the ROMP of cyclooctadiene. The ROMP was carried out with Grubbs second generation catalyst and the POSS-terminated PCOD telechelics with variable lengths of PCOD were obtained by controlling the molar ratios of CTA to cyclooctadiene. All the POSS-terminated PCOD telechelics in bulks were microphase-separated; the morphologies were quite dependent on the lengths of PCOD midchains. The POSS end groups can promote the crystallization of PCOD chains at room temperature, which was in marked contrast to the case of plain PCOD. Compared to the plain PCOD, the POSS-terminated PCOD telechelics displayed improved thermal stability and surface hydrophobicity. (C) 2016 Wiley Periodicals, Inc.