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Further development of next-generation block copolymer (BCP) lithography processes is contingent on comprehensive studies of the ordering dynamics of high-ﾏ� BCPs that can form sub-10 nm features on thin films. However, quantitative analyses of the degree of ordering on the surface and cross sections of thin films have been difficult to execute. To tackle this challenge, we employ a perpendicular lamella-forming high-ﾏ� BCP, poly(polyhedral oligomeric silsesquixone-block-2,2,2-trifluoroethyl methacrylate) (PMAPOSS-b-PTFEMA), and reveal that the high-ﾏ� PMAPOSS-b-PTFEMA requires three times the activation energy (Ea) compared to that of poly(styrene-block-methyl methacrylate) (PS-b-PMMA) for defect annihilation, at Ea = 2600 ﾂｱ 420 kJ mol窶�1, and a transition from a fast ordering regime with a growth exponent of ﾎｦ = 0.30 at lower orientational order parameters (ﾏ�2 < 0.36) to a slow ordering regime with ﾎｦ < 0.05 at ﾏ�2 > 0.36, where well-aligned lamellae restrict defect annihilations to enthalpically unfavorable glide mechanisms that require BCP intermixing.