The invention discloses a preparation method of high-purity large-particle-size silica sol, which belongs to the technical field of silica sol preparation. The specific preparation method comprises the following steps of mixing an acidic silica sol solution with a pH value of 2-3 with polyethylene glycol 2000-10000, adjusting the pH value to 8-9.5, and heating and boiling to obtain sol crystal grains, adding acid activated resin, washing the resin until the pH value is 3.0-4.5, adding an aluminum salt modifier and water glass, and carrying out ion exchange reaction on the water glass to obtainaluminum modified silicic acid, and adding aluminum modified silicic acid into the sol crystal grains, adding an alkaline solution to adjust the pH value to 9.5-10.5, synthesizing while performing ultrafiltration, and heating to synthesize the high-purity large-particle-size silica sol. The acidic silica sol is subjected to hydroxylation reaction, so that the gel is aggregated to form a large-particle silica sol matrix, the water glass is used as a raw material, the aluminum-modified active silicic acid is prepared by adopting an ion exchange method, ultrafiltration and synthesis are carriedout simultaneously, the particle size is increased quickly, the energy consumption is low, the synthesis period is short, the production efficiency is improved, and the polishing requirements of noveldevices in electronic industry can be met.