Four supported catalysts, nickel and ruthenium on a HZSM-5 support, were prepared by equal volume impregnation and in-situ decomposition of carbonyl nickel. The properties of catalysts were investigated by catalytic hydro-conversion of 2,2′-dinaphthyl ether as the model compound and extraction residue of Naomaohu lignite as the sample under an initial H₂ pressure of 5 MPa and temperature at 150 °C. According to the catalytic hydro-conversion results of the model compound, Ni−Ru/HZSM-5 exhibited the best catalytic performance. It not only activated H₂ into H···H, but also further heterolytically split H···H into immobile H^‒ attached on the acidic centers of Ni−Ru/HZSM-5 and relatively mobile H⁺. Catalytic hydro-conversion of the extraction residue from Naomaohu lignite was further examined over the optimized catalyst, Ni−Ru/HZSM-5. Detailed molecular compositions of products from the extraction residue with and without hydrogenation were characterized by Fourier transform infrared spectroscopy and gas chromatography/mass spectrometry. The analytical results showed that the oxygen-containing functional groups in products of hydrogenated extraction residue were obviously reduced after the catalytic treatment. The relative content of oxygenates in the product with catalytic treatment was 18.57% lower than that in the product without catalytic treatment.