The silica contained in biomass is generally recovered from the ashes after combustion. In this study, the main objective was the recovery of silica from wheat straw, without degrading the other biomass components. To achieve this goal, the wheat straw was first pre-treated by an acidic organosolv process to separate it into its three major components: cellulose, lignin, and hemicelluloses. The silica, due to the pre-treatment conditions, was in the cellulose fraction, from which it was extracted, under alkaline conditions. The goal was to recover pure silica with suitable particle size and BET surface area, enabling its use in various industrial applications. The extraction and precipitation steps of silica recovery were studied. After optimization, the silica extraction conditions were set at pH 9 to 10 and 85 °C and the precipitation at pH 5 to 5.5. In these conditions, up to 82% of total silica in straw was extracted with high purity, an average particle size of 4 µm, and a BET surface area of 156 m2/g. In summary, silica can be extracted from lignocellulosic biomass, at high yield and purity, without affecting the biorefinery co-products’ yields and quality.