The invention discloses a preparation method of a lightweight thermal insulating wall material of expanded perlite-SiO2 aerogel. The preparation method comprises the following steps of by taking TEOSas a precursor, EtOh as a solvent and H2SO4 and NJ3.H2O as catalysts, adopting acid/alkali two-step catalytic reaction to prepare SiO2 sol, then stirring the SiO2 sol until the sol turns into gel, performing ageing, solvent exchange, surface modification and online temperature raising drying, mixing coal ash, water glass, a polyurethane foaming agent and cement with a product, adding a mixture ina mixer, adding a proper amount of water, uniformly stirring and mixing, performing maintenance to prepare a thermal insulation block, standing for a period of time under the natural condition, and then sending a the thermal insulation block into an autoclave reaction kettle for maintenance to prepare the lightweight thermal insulating wall material. By adopting the preparation method provided bythe invention, in the production process of a novel coal ash porous thermal insulation material, the energy is saved, the main raw material is a solid waste, the cost is low, and the manufactured thermal insulation material accords with the quality requirement with the strength and the thermal insulation performance reaching the standard.