Rice starch–water suspension (20%) were subjected to high hydrostatic pressure (HHP) treatment at 120, 240, 360, 480, and 600 MPa for 30 min. Polarizing light microscope, scanning electron microscopy (SEM), rapid visco analyzer (RVA), differential scanning calorimeter (DSC), and X-ray diffraction were used to investigate the physicochemical and structural changes of starch. Microscopy studies showed that the treatment of starch with HHP under 600 MPa for 30 min resulted in a complete loss of birefringence and a gel-like appearance. The treatment of starch suspension with HHP at 600 MPa resulted in a significant increase in swelling power and solubility at low temperature (50–60 °C), but opposite trends were found at high temperature (70–90 °C). The DSC analysis showed a decrease in gelatinization temperatures and gelatinization enthalpy with increase of pressure levels. RVA viscograms of starches exhibited an increase in peak, trough, and final viscosities, peak time, and pasting temperature but decrease of breakdown, setback viscosities, and pasting temperature when pressure was increased. X-ray diffraction studies showed that the HHP treatment converted rice starch that displayed the A-type X-ray patterns to the B-type-like pattern. These results showed that the treatment of rice starch in 20% starch/water suspension at a pressure of 600 MPa for 30 min led to a complete gelatinization of starch granules.