Porous starch is produced by enzymatic hydrolysis of rice starch at subgelatinization temperatures, applying reaction times of 3, 6, and 12 h, respectively. The effects of α-amylase (AM), amyloglucosidase (AMG), and their mixture (AM þ AMG) on starch are studied by morphology, hierarchical porosity, granular structure, and thermal and surface stability. The reaction time of 6 h is found to be the most appropriate for the three enzymatic treatments studied. The techniques used to characterize the porous starches reveal porosity distribution is present in all samples. It is possible to identify the presence of macropores (scanning electron microscopy), mesopores (porosimetry of nitrogen), and micropores (adsorption capacity). The addition of AM suggests the formation of a higher micropore fractions, whereas the AM þ AMG mixture contributes to the development of more mesopore and macropore fractions. The particle size distribution, gelatinization temperatures, and zeta potential modulus results indicate that porous starches prepared in this way, can be useful as a thermoresistant and stable adsorbent in food and chemical applications.Results are expressed as the average value and standard error of the mean, thermal properties (two replicates) and surface properties (three replicates). Values followed by different letters within a column denote significant differences (P < 0.05).