Pt nanoparticle with high Pt-Pt coordination number and degenerate d orbitals, has a strong affinity to naphtha and relevant intermediates, leading to severe carbon deposition and catalyst deactivation during naphtha reforming. The catalytic performance of Pt catalyst could be finely tuned by tailoring its d-electron structure. Herein, we propose a straightforward chlorinating strategy to transform PtOx nanoparticle into Pt single atoms with a specific Cl-Pt-O coordination. The adsorption of benzene on Pt is weakened with the Cl-Pt-O coordination, which facilitates aromatics desorption and hampers carbon deposition. Density functional theory (DFT) calculation indicates that the z-axis of Pt 5d orbitals is occupied and selectively exposes xy-plane orbital (dxy and dx2-y2), which weakens d-π hybridization between Pt 5d orbitals and π orbital of benzene ring. The d-electron regulation through chlorinating is a readily scalable strategy to synthesis single atom catalysts, and optimize naphtha reforming catalytic performance.