Rice husk is a bulky byproduct with a high silica content from rice milling. In this study, the application of an acid-catalyzed ionic liquid (IL) pretreatment was studied for processing rice husks with a rugged structure. The pretreatment conditions were 130°C for 30 min with 1.2 wt% HCl. The results of enzymatic hydrolysis demonstrated that cellulose conversion of HCl-BMIMCl-treated at 48 h was increased by 660.05%, 538.81%, and 376.55% compared with the untreated, HCl-treated, and BMIMCl-treated rice husks, respectively. Composition analysis demonstrated that most of the hemicellulose was removed in the acid-IL combined treatment. Moreover, scanning electron microscopy, X-ray diffraction (XRD), and Fourier transform infrared analyses indicated that the crystalline structure and outer silica layer of the rice husks were efficiently broken up. The results revealed that the HCl-catalyzed dissolution is highly favorable for the industrial application of rick husks in the production of fermentable sugar and high-purity silica.