In this study, nitrogen fixation in the electrolyte was achieved by atmospheric pressure non-thermal plasma generated by a sinusoidal power supply (with an applied voltage of 10 kV and frequency of 33 kHz). Ammonia measurements on plasma exposed electrolyte at several working gas and purging gas conditions revealed that nitrogen plasma in the same gas environment is more favourable for plasma-assisted ammonia synthesis. In addition, photo-electrochemical water splitting was performed by irradiating UV light on a titanium dioxide semiconductor photo-anode to generate hydrogen donor in nitrogen reduction reaction. The amount of ammonia synthesized by this synergistic process of photo-electrochemical water splitting and nitrogen plasma is six times higher than that obtained by nitrogen plasma alone. An increase in the co-synthesized NOX concentrations and background contamination at reaction site reduces the ammonia synthesis rate and Faraday efficiency. However, the ammonia production efficiency was increased up to 72% by using a proton-exchange membrane which prevents the diffusion of oxygen evolved from water splitting into the plasma, and by reducing the axial distance between the plasma electrode and reaction site. The sustainable nitrogen fixation process reported herein can be performed at atmospheric pressure conditions without a direct input of hydrogen gas or any catalyst.