A polymethylpentene film loaded with toluene is being developed as a reference material to support the reliable measurement of volatile organic compound emissions from building materials using environmental chambers. Earlier studies included the measurement of the material-phase diffusion coefficient (D) and material/air partition coefficient (K) at 23°C. A fundamental mass-transfer model can then be used to predict toluene emissions from the reference material at 23°C, serving as a reference for validating chamber-measured emission profiles. In this study, the effect of temperature and humidity on performance of the reference material was investigated. Reference material emissions were measured at 10, 23, and 30°C and at different relative humidity (RH) levels. D and K at different temperatures and RH were determined using an independent method. Results showed that RH does not significantly affect D and K and had no effect on emissions. However, emissions increased substantially at elevated temperatures due to the relationship between D and temperature. A statistical analysis shows good agreement between model-predicted and measured gas-phase concentrations, indicating that the model can accurately predict emission profiles as a function of temperature. The reference material can therefore be applied to a wide range of emission chamber testing conditions.