The objective of this study was to understand the resistant-starch (RS) formation during kernel development of a high-amylose maize, GEMS-0067 line. The RS content of the starch, determined using AOAC method 991.43 for total dietary fiber, increased with kernel maturation and increase in the amylose/intermediate component (IC) content of the starch. Gelatinization of the native starches showed a major thermal transition with peak temperature at 76.6-81.0 degrees C. An additional peak ( approximately 97.1 degrees C) first appeared 20 days after pollination and then developed into a significant peak on later dates. After removal of lipids from the starch, this peak disappeared, but the conclusion gelatinization temperature remained the same. The proportion of the enthalpy change of the thermal transition above 95 degrees C, calculated from the thermogram of the defatted starch, increased with kernel maturation and was significantly correlated with the RS content of the starch (r = 0.98). These results showed that the increase in crystallites of amylose/IC long-chain double helices in the starch resulted in the increase in the RS content of the starch during kernel development.