This study demonstrates the application of two-dimensional correlation analysis to evaluate the effect of different temperatures on the headspace of wines analysed using a mass spectrometry electronicnose instrument in order to obtain their fingerprint. We have demonstrated that for a complex sample matrix such as wine, selection of an optimum sampling temperature of the headspace will be critical.Additionally, it was observed that small changes in headspace temperature can have a significant effect on the classification or fingerprint of wines analysed. Overall, the fingerprint of the red wine volatiles collected from the headspace seems to be less affected by temperature, while white wines are more affected by changes in volatile compounds present in the wine matrix. It was highlighted that both wine types had different behaviour in response to temperature changes in the headspace. The practical implication of this study is that care in the selection of the optimal temperature should be exercised when obtaining the MS fingerprint of wines using headspace.