The granules of high-amylose maize starches swelled slightly at 100 °C and swelled remarkably at approximately 120 °C. The destruction of starch structure begins at the center and expands rapidly to the periphery. A few Maltese crosses were still maintained especially in small-sized granules when heated at 120 °C. The small-sized granules of high-amylose starch had significantly higher amylose contents than large-sized granules. The starch granules treated at 140 °C were significantly destroyed.