LiNiO2-coated Ni sheet anodes were prepared by a sol-gel coating method and an atmospheric plasma-spraying technique, and were used in electrolytic production of (CF3)(3)N in a room-temperature molten fluoride (CH3)(4)NF center dot 4.0HF. LixNi2-xO2 thin films of x=0.6-0.8 were successfully formed on Ni sheets by the sol-gel coating methods. The LiNiO2 film prepared by atmospheric plasma-spraying technique had nearly the stoichiometric composition (x approximate to 1). These LiNiO2-coated Ni sheet anodes gave lower anode potentials than pure Ni anode during electrolysis, because the presence of the LiNiO2 layer suppressed the formation of NiF2 insulation layer and the electronic conductivity of the former was much higher than that of the latter. The maximum mole fraction of (CF3)(3)N of 33% in the anode gas was obtained in electrolysis using the plasma-sprayed LiNiO2-coated Ni sheet anode at 20 mA cm(-2) in the (CH3)(4)NF center dot 4.0HF melt. The anodic potential under the above conditions was 4.13 V after electrolysis for 100 h, which was the lowest of all experiments. Consequently, stoichiometric LiNiO2-coated Ni sheet was the most preferable anode material for the electrolytic (CF3)(3)N synthesis in the (CH3)(4)NF center dot 4.0HF melt.