Cassava starch is modified to increase porosity and lacerations that are limited when only enzymatic treatments are used. This study proposes to improve enzymatic activity of α-amylase and amyloglucosidase on the polymer chains of cassava starch by implementing physical and thermal pretreatments below the gelatinization temperature and before the hydrolytic process. The pretreatments increased the biocatalytic action of the enzymes, causing significant changes in the morphology of the granules, and superficial lacerations were found in samples of starches pretreated with ultrasound (UTS) or annealing and ultra-rapid freezing (ANN-C). At the structural level, the modified starches revealed substantial changes as the infrared spectra reflected a displacement of the absorption bands in the region from 900 to 1100 cm-1. This is associated with an alteration and reorganization of the amorphous and crystalline zones of the granules and is consistent with a decrease in amylose content (from 19.53% to 17.64%) and an increase in the crystallinity index. The thermal behavior of the starches was also modified by increasing the peak temperature (from 68.22°C to 75.38°C) and reducing the gelatinization enthalpy (from 19.34 to 15.79 J/g). UTS and ANN-C pretreatments significantly improved the mesoporous and hydrophilic properties of the modified cassava starches.