AbstractUltrafast ionization of atoms or molecules by intense laser pulses creates extremely non-stationary ionic states. This process triggers attosecond correlated electron-hole dynamics and subsequent ultrafast non-equilibrium evolution of matters. Here we investigate the interwoven dynamic evolutions of neutral nitrogen molecules together with nitrogen ions created through transient tunnel ionization in an intense laser field. Based on the proposed theoretical frame, it is found that nitrogen molecular ions are primarily populated in the electronically excited states, rather than staying in the ground state as predicted by the well-known tunneling theory. The unexpected result is attributed to sub-cycle switch-on of time-dependent polarization by transient ionization and dynamic Stark shift mediated near-resonant multiphoton transitions. These findings corroborate the mechanism of nitrogen molecular ion lasing and are likely to be universal. The present work opens a route to explore the important role of transient ionization injection in strong-field induced non-equilibrium dynamics.