This work aims to study the ignition enhancement of hybrid nanosecond-pulsed and DC discharges at atmospheric pressure using numerical modeling of CH4/O2 mixtures. A hybrid time splitting method comprising ZDPlasKin and CHEMKIN as well as a plasma mechanism incorporating vibrationally excited species and low temperature CH4 oxidation pathways of O2 (a1 ∆g) are developed and validated. The results show that the hybrid discharge is more efficient in ignition enhancement than thermal ignition. The vibrationally excited species and O2 (a1 ∆g) are generated efficiently by non-equilibrium excitation in the hybrid discharge. It is found that O2 (a1 ∆g) shortens the ignition delay time effectively, whereas CH4(v) and O2(v) contribute to the ignition enhancement by slow gas heating. It is shown that the selective production of active species can be realized at different DC electric field strengths and there exists an optimal condition enhancing the ignition.