This work presents a novel hydrothermally aided sol-gel method for preparation of mesoporous silica nanoparticles (MSNs) with a narrow particle size distribution and varied pore sizes. The method was carried out in alkaline media in presence of polyethylene glycol (PEG) and cetyltrimethylammonium chloride (CTAC) as dual templates and permitted the synthesis of spherical mesoporous silica with a high surface area (1011.42 m2/g). The MSN materials were characterized by FTIR, Thermogravimetric (TG), Nitrogen adsorption and desorption and Field emission scanning electron microscopic analysis (FESEM). The materials feasibility as solid phase adsorbent has been demonstrated using cationic dyes; Rhodamine B (RB) and methylene blue (MB) as models. Due to the large surface area and variable pore width, the adsorption behaviors toward cationic dyes showed outstanding removal efficiency and a rapid sorption rate. The adsorption isotherms of RB and MB were well-fitted to the Langmuir and Freundlich models, while the kinetic behaviours adhered closely to the pseudo-second-order pattern. The maximum adsorption capacities were determined to be 256 mg/g for MB and 110.3 mg/g for RB. The findings suggest that MSNs hold significant potential as solid-phase nanosorbents for the extraction and purification of dye pollutants, particularly in the analysis and treatment of effluents containing cationic dyes.