The synthesis of a series of poly(POSS-NBE-b-MTD) copolymers was successfully accomplished, taking advantage of sequential, ring-opening, metathesis block copolymerization using $RuCl_2(=CHPh)(PCy_3)_2$ catalyst. By using cyclopentyl-POSS-norbornene (POSS-NBE) monomer as the first block in the block copolymer, living poly(POSS-NBE) with controlled molecular weight and narrow molecular weight distribution was produced. Then, poly(POSS-NBE-b-MTD) copolymers were successfully prepared, in which sequential monomer addition of methyltetracyclododecene (MTD) to the living poly(POSS-NBE) chain ends was utilized to achieve quantitative crossover efficiency. Characterization by $^1H$ NMR spectroscopy and GPC confirmed the high definition and structural integrity of the poly(PO$S-NBE-b-MTD) copolymers. Thermal properties-and morphologies of the POSS-containing block copolymer nanocomposites were also investigated by using thermogravimetric analysis (TGA), transmission electron microscopy (TEM), and wide-angle X-ray scattering (WAXS).