In this article we describe a new approach to enhance presence technologies. First, we discuss the strong relationship between cognitive processes and emotions and how human physiology is uniquely affected when experiencing each emotion. Secondly, we introduce our prototype multimodal affective user interface. In the remainder of the paper we describe the emotion elicitation experiment we designed and conducted and the algorithms we implemented to analyse the physiological signals associated with emotions. These algorithms can then be used to recognise the affective states of users from physiological data collected via non-invasive technologies. The affective intelligent user interfaces we plan to create will adapt to user affect dynamically in the current context, thus providing enhanced social presence.