In this paper the rotational temperature of OH(A-X) and rotational population distribution of OH(A) are investigated for streamer discharges in bubbles and glow discharges with liquid electrodes, both at atmospheric pressure. The influence of the filling gas is investigated in detail and the non-Boltzmann nature of the rotational population distributions is discussed. It is shown that the rotational population distribution of OH(A) is even at atmospheric pressure an image of the formation process or is at least influenced by it. As a consequence the rotational temperature is in this case not a good estimate of the gas temperature as the rotational population distribution is not an image of a kinetic temperature. In some cases rotational states with small rotational numbers offer a possibility to obtain the gas temperature. The influence of these results on the determination of gas temperatures in the field of liquid plasmas is discussed. © 2009 WILEY-VCH Verlag GmbH & Co. KGaA.