In a study of the surface morphology of commercial poly(vinyl acetate-co-vinyl alcohol) (ACA copolymer) with different percents of hydrolysis, different structures like fibrils, spherulites, micelles, vesicles, and spheroids were seen. The copolymer was crystallized by annealing at two different temperatures. The morphology of the polymer after crystallization and also without crystallization was studied. A decrease in the melting temperature just by heating to the melting temperature was observed, and for a detailed study, repetitive heating of the copolymer was carried out and changes in the mass and heat of fusion after every heating was recorded. The morphology of the copolymer after repetitive heating was studied.