We report for the first time a photothermal paper sensor for the selective and sensitive detection of 2,4,6-trinitrotoluene (TNT) down to 14 ng/cm(2). In the presence of TNT, a Meisenheimer complex was formed by means of a charge transfer process from an electron-rich group in polyaniline (PANI) to an electron-deficient nitro group in TNT, which resulted in the near-infrared absorption around 800 nm. Upon irradiation with an 808 nm diode laser, the photothermal effect of the PANI/TNT complex caused the temperature increase, and the temperature difference (ΔT) was proportional to the TNT concentration, while the temperature increase was hardly observed for other nitroaromatics including 2,4-dinitrotoluene (DNT), 2,4,6-trinitrophenol (TNP), and nitrobenzene (NB), affording high selectivity toward TNT. All the tests can be conducted both in solution and on paper. Therefore, the proposed photothermal strategy not only offers a fast and convenient protocol for selective detection of TNT but also indicates great potential in practical applications, especially for airport/railway security inspection and prevention of terrorist attacks.