Electrochemical synthesis of ammonia from water vapour and nitrogen was investigated using an electrolytic cell based on CoFe 2 O 4 –Ce0 .8 Gd 0.18 Ca 0.02 O 2−δ (CFO-CGDC), CGDC-ternary carbonate composite and Sm 0.5 Sr 0.5 CoO 3−δ –Ce 0.8 Gd 0.18 Ca 0.02 O 2−δ (SSCo-CGDC) as cathode, electrolyte and anode respectively. CoFe 2 O 4 , CGDC and SCCo were prepared via a combined EDTA-citrate complexing sol–gel and characterised by X-ray diffraction (XRD). The AC ionic conductivities of the CGDC-carbonate composite were investigated under three different atmospheres (air, dry O 2 and wet 5% H 2 –Ar). A tri-layer electrolytic cell was fabricated by a cost-effective one-step dry-pressing and co-firing process. Ammonia was successfully synthesised from water vapour and nitrogen under atmospheric pressure and the maximum rate of ammonia production was found to be 6.5 × 10 −11 mol s −1 cm −2 at 400 °C and 1.6 V which is two orders of magnitude higher than that of previous report when ammonia was synthesised from N 2 and H 2 O at 650 °C.