The invention discloses a solid silicon-based Waugh-type molybdenum-containing heteropolyacid catalyst and application thereof. A preparation method for the solid silicon-based Waugh-type molybdenum-containing heteropolyacid catalyst comprises the following steps: adding a siliceous porous material and an amido functional group coupling agent into a dilute acid solution with a pH value of 3-4, carrying out magnetic stirring at room temperature for 12-24 h, then adding Waugh-type molybdenum-containing heteropoly acid and a surfactant, performing ultrasonic oscillation for 0.5-1 h, transferringthe formed substance into a hydrothermal reactor, raising a reaction temperature from room temperature to 150-180 DEG C within 0.5-1 h by using a temperature-programmed oven, keeping the temperature for 48-72 h, then carrying out natural cooling to room temperature, performing rinsing with ultrapure water and ethanol several times separately, and carrying out filtering and drying for 10-12 h. Thecatalyst of the invention can efficiently catalyze hydrogen peroxide to oxidize iodine ions under heterogeneous conditions so as to produce elemental iodine; and the catalyst has the advantages of mild reaction conditions, high utilization rate of hydrogen peroxide, friendliness to environment, no pollution, no peroxidation and good thermal stability, can be repeatedly reused a plurality of times,and is easy to recycle.