The application of midinfrared polarization spectroscopy (mid-IRPS) is demonstrated for sensitive detection of minor molecular species in combustion environments by probing rovibrational transitions. High resolution mid-IRPS spectra of low pressure flames were obtained in the spectral range around 3 microm. Rotational lines of the fundamental vibrational band of the hydroxyl radical (OH) were fully resolved and properly assigned among the abundant hot water lines in the flame mid-IRPS spectra. The high signal-to-noise ratio of the recorded OH lines indicates the feasibility of sensitive mid-IRPS OH detection. This constitutes, to the best of our knowledge, the first reported OH flame detection in the midinfrared spectral range. A simulation of hot water mid-IRPS lines with molecular parameters extracted from the HITRAN/HITEMP database was performed and compared with the observed flame spectra. The proper prediction of the hot water lines may help to clarify the potential spectral interferences associated with minor species measurements.