We propose microporous networks (MPNs) of a light emitting spiro-carbazole based polymer (PSpCz) as luminescent sensor for nitro-aromatic compounds. The MPNs used in this study can be easily synthesized on arbitrarily sized/shaped substrates by simple and low-cost electrochemical deposition. The resulting MPN afford an extremely high specific surface area of 1300 m2/g, more than three orders of magnitude higher than that of the thin films of the respective monomer. We demonstrate, that the luminescence of PSpCz is selectively quenched by nitro-aromatic analytes, e.g. nitrobenzene, 2,4-DNT and TNT. In striking contrast to a control sample based on non-porous spiro-carbazole, which does not show any luminescence quenching upon exposure to TNT at levels of 3 ppm and below, the microporous PSpCz shows a clearly detectable response even at TNT concentrations as low as 5 ppb, clearly demonstrating the advantage of microporous films as luminescent sensors for traces of explosive analytes. This level states the vapor pressure of TNT at room temperature.