This work reports that ammonia (NH(3)) can be used as an efficient co-reactant for tris(2,2'-bipyridine)ruthenium(II) (Ru(bpy)(3)(2+)) electrochemiluminescence (ECL) in ionic liquids (ILs), on the basis of which a signal-on ECL sensor for directly detecting gaseous NH(3) has been developed. The NH(3) ECL sensor has a very high sensitivity, with a detection limit of 10 ppt NH(3) (at signal-to-noise ratio of 3) without any preconcentration. The high sensitivity is mainly due to the zero ECL background of Ru(bpy)(3)(2+) in the ILs, strong co-reactant ECL activity of NH(3), and high solubility of NH(3) in imidazolium-based ILs. Additionally, the ECL sensor shows an excellent selectivity against common interfering gases and a wide linear response range from 10 ppt to 10 ppm.