In the present work, we report the use of regioregular poly(3-hexyltiophene) polymer (RR-P3HT) as a potential light-activated material for sensing the chemical nerve agent simulant dimethyl methylphosphonate (DMMP). The electrical response of thick films of RR-P3HT, deposited by spray-coating method onto a porous laminate substrate at room temperature, to DMMP vapours was investigated. The studied material was activated by light-emitting diodes that emitted light of different wavelengths. The sensing properties of RR-P3HT are considerably enhanced upon exposure to blue and yellow light. However, excitation by the low wavelength light (blue) caused degeneration of the material, resulting in lowered stability. In the case of the yellow light, degeneration was much slower and the limit of detection was 0.4 ppm. The studied material exhibited high selectivity, as it did not respond to 6 ppm of acetone and methanol vapours.