<p>Non-equilibrium plasma-assisted ammonia synthesis is investigated through enhanced active species production with ferroelectric discharge. Time-resolved in-situ diagnostics of femtosecond two-photon absorption laser-induced fluorescence, coherent anti-Stokes Raman scattering, and laser absorption spectroscopy, as well as optical emission spectroscopy, were conducted to probe the key intermediate species, such as H and N radicals as well as N₂(<i>ν</i>), ions, and NH₃ to achieve better understanding of non-equilibrium energy transfer and ammonia formation. The results reveal that ferroelectric discharge improved ammonia yield by four times. Results also show that ferroelectrics not only enhanced ions (N₂⁺) production, radicals (N, H) number density, but also increased the N₂ vibrational temperature. Further plasma modeling identified the couplings between elevated radical and ion production and enhanced vibrational excitation reactions, e.g., N + H₂(<i>ν</i>)→NH + H, N₂(<i>ν</i>)+H → NNH, N₂⁺ + H₂ → H + N₂H⁺, and N₂H⁺+e→NH + N, facilitated by ferroelectric discharge. These findings provide critical insight into the mechanism of ferroelectric plasma catalysis and highlight their potential in advancing energy-efficient chemical synthesis.</p>