In the study, the desilication liquids and acid‐leached residues derived from the “alumina extraction process” of coal fly ash (CFA) were used as raw materials to prepare sodium silicate precursor. Then, the mesoporous silica with controllable pore structure properties was synthesized by an efficient, template‐free process from obtained sodium silicate. The effect of the sodium silicate properties and synthesis conditions on the pore structure properties of disordered mesoporous silica were investigated. The resulting material was characterized by N2 adsorption–desorption, scanning electron microscopy (SEM), and transmission electron microscopy (TEM) and tested as an adsorbent for removal of lead ions (Pb2+). The results showed that the precursor with high modulus (3.0) and concentration (60 g·L−1) was beneficial for the synthesis of mesoporous silica with high specific surface area. The mesoporous silica with specific surface area of 690 m2·g−1 and pore volume of 1.28 cm3·g−1 was synthesized at mild aging temperature (40°C) and pH value of 8. Moreover, the materials possessed an adsorption capacity of 303 mg·g−1 for lead ions after amino modification. The adsorption efficiencies for lead ions were maintained at ~90% after five recovery cycles. Overall, the utilization efficiency of SiO2 in CFA reached up to 93%.