Boron nitride nanosheets (BNNSs) exfoliated from hexagonal boron nitride (h-BN) show great potential in polymer-based composites due to their excellent mechanical properties, highly thermal conductivity, and insulation properties. Moreover, the structural optimization, especially the surface hydroxylation, of BNNSs is of importance to promote their reinforcements and optimize the compatibility of its polymer matrix. In this work, BNNSs were successfully attracted by oxygen radicals decomposed from di-tert-butylperoxide (TBP) induced by electron beam irradiation and then treated with piranha solution. The structural changes of BNNSs in the modification process were deeply studied, and the results demonstrate that the as-prepared covalently functionalized BNNSs possess abundant surface hydroxyl groups as well as reliable structural integrity. Of particular importance is that the yield rate of the hydroxyl groups is impressive, whereas the usage of organic peroxide and reaction time is greatly reduced due to the positive effect of the electron beam irradiation. The comparisons of PVA/BNNSs nanocomposites further indicate that the hydroxyl-functionalized BNNSs effectively promote mechanical properties and breakdown strength due to the enhanced compatibility and strong two-phase interactions between nanofillers and the polymer matrix, which further verify the application prospects of the novel route proposed in this work.