A convenient and effective route to synthesize the fully conjugated bimetallic complex (Bu4N)(2){tto[Ni(dmit)(2)]}, the starting material for conducting conjugated bimetallic complexes [C](x){tto[Ni(dmit)(2)]}, has been developed. This new method is the direct conversion (Bu4N)(2)[Ni(dmit)(2)] into (Bu4N)(2){tto[Ni(dmit)(2)]} by dithionites. For the first time, the conversion of dmit(2-) into tto(2-) was realized. Also, the structure of a new crystal form of this complex was reported.