(Vinyl acetate)/(ethyl acrylate) (V/E) and (vinyl acetate)/(butyl acrylate) (V/B) copolymers were prepared by free radical solution polymerization. H-1-NMR spectra of copolymers were used for calculation of copolymer composition. The copolymer composition data were used for determining reactivity ratios for the copolymerization of vinyl acetate with ethyl acrylate and butyl acrylate by Kelen-Tudos (KT) and nonlinear Error in Variables methods (EVM). The reactivity ratios obtained are r(v) = 0.03 +/- 0.03, r(E) = 4.68 +/- 1.70 (KT method); r(V) = 0.03 +/- 0.01, r(E) = 4.60 +/- 0.65 (EV method) for (V/E) copolymers and r(V) = 0.03 +/- 0.01, r(B) = 6.67 +/- 2.17 (KT method); r(V) = 0.03 +/- 0.01, r(B) = 7.43 +/- 0.71 (EV method) for (V/B) copolymers. Microstructure was obtained in terms of the distribution of V- and E-centered triads and V- and B-centered triads for (V/E) and (V/B) copolymers respectively. Homonuclear H-1 2D-COSY NMR spectra were also recorded to ascertain the existence of coupling between protons in (V/E) as well as (V/B) copolymers.