Recently, production of a clean sulfur-free fuel and related green chemical processes have attracted the attention of researchers. The development of efficient desulfurizers is an effective strategy to meet this demand. Herein, a facile method to successfully construct W18O49 nanoneedles (NNs) coupled with Pt species by a spontaneous redox reaction between reductive supports and oxidative platinum precursors was revealed. The closely arranged NNs hybrids with strong metal-support electron interaction and in situ-derived carbon are successfully constructed. The Pt species are stabilized on the defective W18O49 NNs surface, which accelerates the adsorption and activation of molecular oxygen. The monolithic catalyst promotes the oxidation conversion of dibenzothiophene in the process of catalytic reactive-type desulfurization. By adjusting the reaction conditions, the catalyst shows over 99.0% dibenzothiophene conversion at only 0.8% Pt loading, and the polar products can be completely removed by extraction. Also, the catalyst showed a relatively stable regeneration and reused performance.