The invention discloses a zeolite molecular sieve as well as preparation method and application thereof, and belongs to the field of chemical technology. In the invention, V-Si-ZSM-22 zeolite molecular sieves different in vanadium content (0-25%) are synthesized by an ionic liquid dry glue method, wherein the vanadium species exists mainly in a form of chained poly VO3<-> and is connected with a zeolite framework through a vanadium-oxygen bond to be applied to a rapid hydroxylation reaction of arene; in an ideal condition that the substrate and hydrogen peroxide have an equal molar ratio, a high yield of phenol products is obtained within a reaction time of 30 seconds. The catalyst adopted in the invention is easy to prepare; the reaction time is extremely short, and thus the reaction is efficient and energy-saving; the yield of phenol products is high, and fewer byproducts are generated; with the hydrogen peroxide as an oxidizing agent, the economic cost and environmental cost are low; the product is easily separated from the catalyst, and the aftertreatment is simple; the catalyst is easy to use repeatedly and thus is green and environmentally friendly, and has a very important application prospect.