Correlation between hydrogen-bonding self-association and sequence distribution in poly(vinyl acetate-co-vinyl alcohol) copolymers (ACA) with different degrees of basic hydrolysis and sequence distributions has been studied by thermal analysis and NMR spectroscopy. C-13 NMR spectroscopy has also been used to elucidate the blocky nature, branching, and tacticity of the copolymers. Thermal analytical studies indicate that hydrogen bonding distribution in black alcohol and vinyl acetate copolymers strongly depend on the sequence distribution wherein hydroxyl-hydroxyl self-association is preferred.