Advanced modern multidimensional solution NMR experiments have been used to deduce the sequence distribution in poly(VDF-co-HFP) copolymers. Assignment of F-19 resonances from different monomer- and regio-sequences in poly(VDF-co-HFP) copolymer were identified. In addition to corroborating some assignments reported in earlier literature, this work provides assignments of some new resonances from the spectra of poly(VDF-co-HFP) copolymer, which resulted from better dispersion of the resonances. These assignments are used for the monomer sequence analyses of two polymers using first-order Markovian statistics, and the relative reactivities of the monomers during polymerization are discussed. The results from this study provide insight into the polymerization chemistry for this fluoropolymer.