Nonequilibrium plasma has a great potential in the lean combustion of gasoline engines. However, fundamental studies on plasma‐assisted combustion on gasoline components are limited. In the present study, Low‐temperature oxidation behaviors for n‐heptane and iso‐octane in a plasma flow reactor were investigated. Species measurements were performed at room temperature and low pressure of 40 mbar using the electron ionization molecular‐beam mass spectrometry (EI‐MBMS). A total of 72 and 57 species were quantified in n‐heptane and iso‐octane oxidation, respectively. Based on measured species data, reaction networks of n‐heptane and iso‐octane in the plasma system were discussed. Particularly, some typical low‐temperature intermediates, such as cyclic ethers, diones, and ketohydroperoxides, were observed, suggesting the applicability of the classical low‐temperature reaction scheme in the plasma system of large hydrocarbons. The results indicate that the major role of plasma discharge on the low‐temperature oxidation of large hydrocarbons is either to breakdown large fuel molecules or to accelerate the chain initiation reactions. We also investigated the parametric effects of voltage, frequency, and residence time on the species pools, and found that the increase of these parameters leads to higher production of intermediates. The whole system reactivity was most sensitive to the plasma voltage. The difference between plasma frequency and residence time on the species formation was found. Moreover, some highly temperature‐sensitive reactions, such as the RO2 → QOOH, proceed at very low temperatures (around 340 K) in the plasma system, which was potentially attributed to the additional energy from plasma‐generated species.