Nitrogen molecular ions (N2 +) in air plasma pumped by femtosecond laser pulses give rise to superradiant emission at 391.4 nm in the presence of an external seed pulse at proper wavelength. Due to the transient alignment of the nitrogen molecular ions, the superradiance signal presents a strong modulation as a function of the temporal delay between the pump and the seed pulses. Through Fourier transformation with high frequency resolution, we distinguished the contribution of the finely separated rotation levels of the upper and lower states. It was found that the population density of certain rotational levels in the upper state is higher than that in the lower one, indicating that population inversion of the rotation levels of the two involved states is a key enabling factor for this superradiant emission.