In this contribution RF excited atmospheric pressure glow discharges are investigated in He–water mixtures in a parallel metal plate reactor by mass spectrometry. Positive and negative ion fluxes to the electrode are investigated as a function of varying water concentration and discharge power. The dominant positive ions are H3O+ (and its clusters), OH+, O+, O2+ , He2+, HeH+, O2+ and H3+. Negative ions are detectable from a concentration of 900 ppm water in He onwards. Coinciding with the emergence of the negative ions, there is a drop in positive ion flux to the mass spectrometer and a significant increase in applied voltage indicating increasing electron loss by attachment and ion loss by mutual (three and two body) positive–negative ion recombination. The dominant negative ions are OH- and its clusters. The negative ion flux increases with increasing water concentration. Positive and negative ion cluster formation increases with decreasing discharge power and increasing concentration of water vapour at constant power. It is shown that the size of the sampling orifice of the inlet of the mass spectrometer is important for sampling atmospheric pressure active plasmas due to the presence of the narrow sheath.