Nitro-aromatic compounds could be sensitively detected by employing cyclic voltammetric experiments in ultrathin TiO2 gel/cyclodextrin (CD) multilayered films that were prepared via the gas-phase surface sol-gel process. Among others, 2,4-DNT showed the highest voltammetric response for the gamma-CD immobilized TiO2 film and its detection limit was estimated to be less than nM levels.