This paper discusses a systematic experimental study of the effects of operating conditions (i.e. relative humidity and temperature of working air streams) on the transport of water vapor and CO2 (as a major indoor air contaminant) through a series of standard polymeric materials suitable for membrane media used in ERVs’. Results are reported for the permeation experiments of binary mixtures of water vapor and CO2 in five commercial polymers of two major types (glassy and rubber). The selectivity of water vapor over CO2 was also evaluated from permeation experiments. In general, the permeability results suggest that ERV exchangers using polymer membranes can achieve high latent effectiveness (i.e. very high water vapor permeability) over a wide range of operating temperature and relative humidity while maintaining very low CO2 permeability and very low EATR crossover rates (<1%) accordingly.