Molecular dynamics (MD) computations predict that the extent of gauche-character for poly(vinylidene fluoride) (PVDF) is greater than that of its 50 mol% copolymer with trifluoroethylene, at both high temperatures and after annealing. PVDF is enriched in gauche-conformations upon cooling whereas the copolymer is enriched in trans-conformations. The MD results are consistent with the experimental trends observed for these polymers.