A preparation method of arylboronic acid catechol ester modified phenolic resin comprises the steps that a boric acid catechol ester compound is added to phenolic resin under an inert atmosphere, heat treatment is performed at the temperature of 110 DEG C for 2 hours after even mixing, then curing is performed at the temperature of 160 DEG C for 2-4 hours to obtain the arylboronic acid catechol ester modified phenolic resin, wherein the mass of the boric acid catechol ester is 1-35% of the mass of the phenolic resin. The adverse influence brought by in-situ formation of a boric acid ester structure of an existing boric acid compound modified phenolic resin is overcome, and a composite material curing process is improved, so that a curing product has a compact structure and good properties, and cured resin has high thermal stability. The resin can be used as a high-performance composite material resin matrix, a carbon/carbon composite material, a high-temperature brake material, a frictional material, a heat insulation material, an adhesive, a coating and a flame retardant material and used in other high-tech fields.