The evolution of volatile compounds was explored in grape berries at fortnightly intervals from fruit-set to late ripening to identify when biosynthetic pathways may be targeted for enhancement of grape and wine aroma. Stepwise linear discriminant analysis (SLDA) fully recognized patterns in berry physiological developmental stages with most of the variance (>99.0%) explained. The preveraison berry developmental stage was identified as a transition stage for volatile compound biosynthesis when most compounds were potentially sequestered to nonvolatile conjugates and berries lost their potential to synthesize esters and terpenes. Terpenes (predominantly eucalyptol, beta-caryophyllene, and alpha-humulene) characterized early berry development, whereas benzene derivatives (2-phenylethanol and 2-phenylethanal) appeared toward late ripening. Furthermore, C(6) volatile compounds changed from acetate esters to aldehydes and finally to alcohols during early, middle, and late berry developmental stages, respectively. The dominance of alcohols in the late stages of berry development, preceded by aldehydes, offers an opportunity for alcohols to aldehydes ratios to be used in the prediction of harvest timing for enhanced grape and wine aroma. The evolution of volatile compounds during berry development suggests a greater dependency on enzyme activity and specificity than extent of fatty acid unsaturation. The dependence of the stage of berry development on the accumulation of the products of alcohol dehydrogenase (ADH), alcohol acetyl transferase (AAT), and enal isomerase enzyme activity from the lipoxygenase pathway raises possibilities for the manipulation of aroma profiles in grapes and wines.