The correlation between hydrogen-bonding self-association and sequence distribution in different poly(vinyl acetate-co-vinyl alcohol) copolymers (ACA) of different degrees of hydrolysis and sequence distributions has been studied by infrared and NMR spectroscopy. For ACA copolymers, quasi-random distributions are obtained by acid alcoholysis, blockier distributions by saponification, and intermediate distributions by a combined method, as shown by C-13 NMR. FTIR spectroscopy has pointed out that hydrogen-bonding distribution in ACA copolymers strongly depends on sequence distribution. For block copolymers, hydroxyl-hydroxyl self-association is preferred, However, in random copolymers, a strong competition between hydroxyl-hydroxyl and hydroxyl-carbonyl association is observed. Hydroxyl-carbonyl association seems to occur between adjacent repeat units, leading to cyclic structures with a high thermal stability.