Hydrogen is widely taken for the most potential clean energy for the moment. Currently, pipeline transport of natural gas mixed with hydrogen is one of the primary approaches of hydrogen transportation. However, compared to pure natural gas (CH4), the explosion and combustion of natural gas mixed with hydrogen may lead to more severe consequences, and its reliability needs to be considered. Existing research of combustion and explosion using methane instead of natural gas have yet to be considered for application to real multi-component natural gas. To address this issue, real multi-component natural gas is configured, and the premixed flame and combustion characterization parameters of natural gas/H2/air are obtained through experiment. The chemical reaction kinetics of natural gas/H2/air mixtures are analyzed using Chemkin Pro software. These results prove that the laminar burning (LB) velocity varies between 0.33 m/s and 2.34 m/s by adding H2. The primitive reactions R1 (H2 + OH → H + H2O) and R3 (H + O2 → O + OH) predominantly contribute to enhancing the LB velocity. The Markstein lengths rang from −0.19 mm to −0.049 mm, most lewis numbers are less than 1, the flame thicknesses and critical destabilization radii are reduced. Additionally, hydrodynamic instability and thermal-diffusion instability are strengthened by adding the hydrogen. As for smaller hydrogen content, the average size of flame cell from about 8 mm program first rises and then falls cyclic fluctuations, fluctuation amplitude gradually reduces, fluctuation frequency accelerates. In larger hydrogen content, this fluctuation amplitude is reduced and the average size of flame cell decreases. In addition, H2 enhances the explosive strength of natural gas. Finally, methane instead of natural gas may exaggerate the velocity of laminar burning and exaggerate or weaken the ignition time delay of natural gas with different hydrogen contents. The current research might provide crucial information for the safe transport of hydrogen mixed with natural gas.