The invention discloses a preparation method of white carbon black with a high structure and a high oil absorption value. The preparation method comprises the following steps: preparing a sodium silicate solution with the modulus of 3.3-3.5 and the concentration of 0.5-1.230 mol/L and sulfuric acid with the mass ratio concentration of 30-60%; the preparation method comprises the following steps: adding water and a sodium silicate solution into a reaction kettle according to a volume ratio of 100: (30-50), adding sodium dodecyl benzene sulfonate, adding sulfuric acid, reacting to form gel, stopping adding acid, and stirring; continuously adding acid to carry out primary reaction, adjusting the pH value to 3.5-5.0, adding a 3-glycidyl ether oxypropyl trimethoxy silane coupling agent to age, stirring at a constant temperature, and dropwise adding sodium silicate to enable the pH value of the suspension to reach 8.0-10.5; stirring while adding a sodium silicate solution and sulfuric acid to carry out secondary reaction, controlling the pH value to be 8.0-10.5, stopping adding sodium silicate after 40-60 minutes, continuously adding sulfuric acid to completely react, uniformly stirring, adjusting the pH value to be 4.0-5.5, and continuously aging; adding a coupling agent, and continuing aging to obtain a suspension; and carrying out washing, solid-liquid separation, pulping and spray drying to obtain a white carbon black product with a high structure and a high oil absorption value. The white carbon black product prepared by the method has the characteristics of high structure and high oil absorption value.