Corn starch dispersions were heated with ethanol (E) and reacted with phytic acid (E-PA), citric acid (E-CA), and a mixture of phytic and citric acid (E-PACA) under dry-heating to prepare heavy metal adsorbents. Microscopy images indicated that ethanol treatment induced the formation of porous structures on the surface; furthermore, treatment with phytic and citric acid induced indentations, pores, and irregular structures in E-PA, E-CA, and E-PACA starches. Phytic and citric acid were retained in the starch molecules through ester bonds with the phosphate and carboxyl groups, respectively. Starch esterification by phytic and citric acid induced a loss of crystallinity, high water absorption capacity, and low solubility. E-PACA starch exhibited more efficient Cu2+ adsorption (38.13 mg/g) than native, E, E-PA, and E-CA starches (0.11, 0.49, 2.05, and 36.23 mg/g, respectively). Thus, modification with ethanol, phytic acid and citric acid can be applied to prepare natural starch-based heavy metal adsorbents.