The genetic types and source of the Lower Paleozoic natural gas in the Ordos Basin in China are controversial, and the geochemical characteristics of light hydrocarbons of natural gas in the fifth member of the Ordovician Majiagou Formation (O1m5) are studied by taking the Daniudi gas field as an example, in order to reveal the gas origin and source. The C5−7 light hydrocarbons are dominated by iso-alkanes rather than the n-alkanes, and the methyl cyclohexane (MCH) content is mostly higher than the nC7 content in C7 light hydrocarbons. The K1 and K2 values range from 1.06 to 1.16 and from 0.33 to 0.81, respectively. The geochemical characteristics of light hydrocarbons indicate that the Lower Paleozoic natural gas in the Daniudi gas field is mainly coal-derived gas which has been generated by the humic source rocks in the Upper Carboniferous Taiyuan Formation (C3t), with insignificant contribution by the O1m sapropelic source rocks. The O1m5 gas pools were accumulated through downward and lateral migration in the free phase. The aromatic contents in C6-7 and nC7/MCH ratios are easily affected by the factors such as water solubilization, adsorption in migration, evaporation, and migration fractionation, therefore, secondary alteration needs to be considered when using these parameters to identify the gas origin.