Aromatic nitroderivatives or ketones react with low valent titanium reagents to give, respectively, the amines or alcohols and coupling products. We have studied, in a non aqueous medium (DMF), the selectivity of a titanium (III) species electrochemically generated from Cp(2)TiC(l)2 for the reduction of the 4,4＇-dinitrodibenzyle and the 9-fluorenone. The cyclic voltammograms of Cp2TiCl2 were registered in the presence of the dinitroderivative or of the ketone. The ESR spectra of the Ti(III) species and of the anion-radicals were monitored under in situ electrolyses. For low values of the ratio [Cp2TiCl2]/[substrate], the macroscale electrolyses performed at the potential of the first step of Cp2TiCl2 yielded selectively the 4-amino-4＇-nitrodibenzyle and the pinacol of the fluorenone. For higher ratios or at a more negative fixed potential, the diamine and the fluorenol become the main reaction products.