The development of sensitive materials for standard and improvised explosives is greatly significant to homeland security. In this paper, the phosphotungstate (NaPT) doped polyphenylene vinylene (PPV) nanotube arrays (NTAs), with excellent optical response, chemical stability, and larger specific surface area, are successfully fabricated by means of the “precursor film” infiltration method. The efficient charge carriers' separation of PPV NTAs can be achieved by doping NaPT to realize the photoelectric detection of explosive vapors. In addition, the identification of six explosives, including ammonium nitrate (AN), dinitrotoluence (DNT), picric acid (PA), p‐nitrotoluene (PNT), triacetone triperoxide (TATP), and trinitrotoluene (TNT), can also be realized through the fingerprint atlas. Moreover, the adsorption energy and excited oscillator intensity has also been employed to explain the interaction between NaPT doped PPV nanotube arrays and various explosive molecules. Obviously, the NaPT doped PPV developed has the potential to be used as an explosive sensor.