The electrochemical reduction of 2,4,6-trinitrotoluene (TNT) was investigated using films of vanadium dioxide. Three distinct reduction peaks were observed in the potential range of -0.50 to -0.90 V (vs an Ag/AgCl reference electrode), corresponding to the electrochemical reduction of the three nitro-groups on the TNT molecule. Adsorptive stripping voltammetry was performed to achieve detection down to 1 μg/L (4.4 nM), revealing a linear response to TNT concentration. These results are the first describing the use of VO2 films as an electrochemical sensor and open new avenues for further electrochemical research using this unique material.