It is essential to improve the low-temperature in-depth oxidation ability and chlorine resistance for catalysts because of reducing the toxic byproducts.Here, a series of S-LaMn1-xO-Snx/Fex catalysts (S: SBA-15, as support) with different d-orbital electron-filled states were rationally designed and used for catalytic combustion of 1,2-dichloroethane (1,2-DCE), Et acetate (EA), and toluene (TOL).Compared with S-LM0.9O-Fe0.1, the S-LM0.9O-Sn0.1 displayed superior low-temperature in-depth activity (T90% = 218.2, 160.3 and 214.3 °C for 1,2-DCE, EA and TOL, resp.) and outstanding chlorine resistance capability.By investigating the relationship between the different d-orbital electron-filled states of catalysts and the toxic byproducts, it is confirmed that Sn 4d orbital with full d electron-filled states can strengthen the electron delocalization around Mn to inhibit the generation of toxic byproducts by weakening the excessively strong binding strength between the Mn-sites and Cl species.Meanwhile, coupling with Sn 4d orbital modulates the d-band structure to strengthen the adsorption and activation of reactants.In addition, In-situ DRIFTS and d. functional theory (DFT) calculation further confirmed the reaction path and mechanism of 1,2-DCE oxidation, as follows: 1,2-DCE→ chloroethanol→ vinyl alc.→ acetaldehyde→ acetic acid→ CO2 and H2O.We believe that this work will provide new promising pathways for designing the catalytic combustion of different (Cl)-VOCs.