A report on the high-performance ambipolar operation in metal-organic thin film transistors (MOTFT) of semiconducting bis(o-diiminobenzosemiquinonate) nickel (II) complex and its derivative, is presented. The study used poly(methylmethacrylate) (PMMA) as the dielectric layer and calcium metal as the source and drain electrodes. A hydroxyl-free polymer or PMMA can decrease the number of electrons traps, while calcium metal with low work function can decrease the injection barrier of the electrons. It was observed during the study that high-performance ambipolar MOTFTs can be prepared by using metal complexes with narrow band gaps and less π-conjugated structures. The study concluded that these metal complexes can be used for the development of high-performance semiconductors.