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The interaction of poly(3-hexylthiophene), P3HT, with oxygen has been investigated. Evidencein the form of UV–vis absorption, electron paramagnetic resonance data, and a field effect conductivity analysis of a polymer-based field effect transistor–is presented for the existence of a reversible charge transfer complex between P3HT and oxygen. Oxygen-sensor applications can be foreseen for thin film transistors incorporating P3HT.