The effects on the internal defects of the rice straw (RS)/high-density polyethylene (HDPE) composites are investigated by removing the extractives with cold water (CW), hot water (HW), and 1% alkaline (AL) solution. The characteristics of the RSs are measured by chemical composition, Fourier transform infrared, X-ray diffractometry, scanning electron microscopy, thermogravimetric analysis, and bulk density testing. The three extractive removal methods change the surface features of the RS and increase the interphase adhesion between the RS and the HDPE matrix. As a result, the inner defects of the RS/HDPE composites are eradicated and the die swell phenomenon disappear. The flexural modulus, flexural strength, and impact strength of the final composites increase by 95.59, 83.29, and 154.79% in the HW extraction method. The CW and the AL extraction also significantly improve the static mechanical properties of the obtained RS/HDPE composites.