The invention discloses a hierarchical-pore titanium silicon molecular sieve catalyst synthesized with the assistance of an aerosol and a preparation method of titanium silicon molecular sieve catalyst, and the titanium silicon molecular sieve catalyst is applied to the catalytic oxidation reaction of cyclohexene. The silicon molecular sieve catalyst is a hierarchical-pore titanium silicon molecular sieve synthesized through an aerosol method, is spherical, contains TS-1 nanometer crystals with MFI micropore structures, and is covered with a porous titanium silicon material. The catalyst can adopt hydrogen peroxide as an oxidant to perform catalytic oxidation on the cyclohexene to synthesize cyclohexene oxide, cyclohexanediol, cyclohexenone and cyclohexanol. The titanium silicon molecular sieve catalyst has the advantages that the preparation process is simple and continuous, the synthesis period is short, the atom utilization ratio is high, the titanium distribution is uniform, and the reaction can be magnified according to a certain ratio. The titanium silicon molecular sieve catalyst provided by the invention has the characteristics of mild reaction conditions, high activity and selectivity, small using amount, and easy recycling.