Copolymerizations of propylene (P) with 1,5-hexadiene (1,5-HD) were carried out with isospecific rac-1,2-ethylenebis(1-indenyl)Zr(NMe2)(2) [rac-(EBI)Zr(NMe2)(2), 1] and syndiospecific isopropylidene(cyclopentadienyl)(9-fluorenyl)ZrMe2 [i-Pr(Cp)-(Flu)ZrMe2, 2] compounds combined with Al(i-Bu)(3)/[Ph-3,C] [B(C6F5)(4)] as a cocatalyst system. Microstructures of poly(propylene-co-1,5-HD) were determined by H-1 NMR, C-13 NMR, Raman spectroscopies and X-ray powder diffraction. The isospecific 1/Al(i-Bu)(3)/[Ph3C][B(C6F6)(4)] catalyst showed much higher polymerization rate than 2/Al(i-Bu)(3)/[Ph3C][B(C6F6)(4)] system, however, the latter system showed higher incorporation of 1,5-HD (r(P) = 8.85, r(1.5-HD) = 0.274) than the former system (r(P) = 16.25, r(P1.5-HD) = 0.34). The high value of r(P) x r(1.5-HD) far above 1 demonstrated that the copolymers obtained by both catalysts are somewhat blocky. The insertion of 1,5-HD proceeded by enantiomorphic site control, however, the diastereoselectivity of the intramolecular cyclization reaction of 1,2-inserted 1,5-HD was independent of the stereospecificity of metallocene compounds, but dependent on the concentration of 1,5-HD in the feed. The insertion of the monomers by enantiomorphic site control could also be realized by Raman spectroscopy and X-ray powder diffraction of the polymers.