The invention relates to a preparation method of a pervaporation film with the preferential penetration of dimethyl carbonate. Film casting liquid containing vinyl polydimethylsiloxane (Vi-PDMS), hydrogen-containing polydimethylsiloxane (H-PDMS), hydrophobic nano SiO2, a catalyst and a solvent is adopted, a film is coated on an upper layer of a porous ultrafiltration film supported by a polyester non-woven fabric, is aired at room temperature and is also heated, and the cross linkage of the film is finished. An additive type polydimethylsiloxane compound film filled with the hydrophobic nano SiO2, which is obtained by the preparation method of the pervaporation film with the preferential penetration of the dimethyl carbonate, has a simple film preparation process, adopts the materials with low price, strong swelling resistance in dimethyl carbonate/methanol azeotropic liquid, and excellent performance of preferential penetration of the dimethyl carbonate. When the filling mass proportion of the hydrophobic nano SiO2 is 15 percent, the separation factor alpha of the pervaporation film is equal to 3.97, and the penetration flux J is equal to 0.707kg/m2h ([DMC]=30wt%, 40 DEG C).