Objectives of this study were to understand how opaque-2 (o2) mutation and quality protein maize (QPM) affect maize kernel composition and starch structure, property, and enzyme digestibility. Kernels of o2 maize contained less protein (9.6−12.5%) than those of the wild-type (WT) counterparts (12.7−13.3%). Kernels of a severe o2 mutant B46o2 also contained less starch (66.9%) than those of B46wt (73.0%). B46o2 and QPM starches contained less amylose (28.0 and 26.0%, respectively) than others (31.9−33.7%). The B46o2 starch also consisted of amylopectin with the fewest branch chains of DP 13−24. Thus, the B46o2 starch was the most susceptible to porcine pancreatic α-amylase (PPA) hydrolysis. Starches of the dry-ground o2maize and QPM were hydrolyzed faster than that of the dry-ground WT maize, resulting from the reduced protein content of the o2-maize kernels and the reduced amylose content of the B46o2 and QPM starch. Starch in the dry-ground maize sample was hydrolyzed faster by PPA (85−91%) than was the isolated starch (62−71%), which could be attributed to the presence of mechanically damaged starch granules and endogenous amylases in the dry-ground maize samples. These results showed that o2 maize and QPM had highly digestible starch and could be desirable for feed and ethanol production.