An electrode modified by a Ti complex in Nafion was used in the electrochemical detection of nitroaromatic compounds (NACs). The catalyst reduced nitroaromatic groups by a six-electron process with a high apparent rate constant, k1, which was estimated to be at least 19 000 mol-1 L s-1 by simulation of the first step of the cathodic reduction of 4-nitrophenylacetic acid, which was used as model molecule. The modified electrode was prepared and optimized in terms of Nafion and catalyst concentrations. In the chosen analytical medium, the Ti-catalyst-containing electrode showed good stability in the presence of nitro species. A standard deviation around 15% was calculated on the analysis performed with 28 different modified electrodes, which could be expected for a drop-coating process. We show that the modified electrode detects several nitroaromatic compounds such as nitrophenols, mononitroaniline, and dinitrotoluene with detection limits ranging from 1 × 10-4 to 9 × 10-4 g L-1 (0.2 × 10-6 to 5.1 × 10-6 mol L-1). As an interesting feature, the sensor exhibits good selectivity toward NAC detection because titanocene does not catalyze the reduction of nitroaliphatic compounds.