The rational design of efficient polar heterogeneous catalysts for oxidation adsorption desulfurization (OADS) is still a challenge. Herein, we fabricated a novel polar fingerprint-like heterogeneous catalyst (HPW-NH2-CPRNSs) by immobilizing phosphotungstic acid on amino grafted phenolic resin nanospheres prepared through gradient temperature hydrothermal method, which exhibits highly effective oxidative-adsorptive desulfurization (OADS) performance. The fingerprint-like nanospheres catalysts were formed when the F127 exposed on the surface of PRNSs was dissolved during the refluxing. Moreover, the polarity of the HPW-NH2-CPRNSs catalysts can be well adjusted by controlling the amount of amino grafting and calcination temperature, which plays an important role in OADS. The removal rate of DBT on optimal polar catalyst reached the highest 98.9% in 90 min. It is the first time that this work involving the phenolic resin polymers have been used as the carrier of desulfurization catalyst and the polarity of the catalyst has been artificially controlled for OADS.