Thermal infrared imaging has been proposed as a potential system for the computational assessment of human autonomic nervous activity and psychophysiological states in a contactless and noninvasive way. Through bioheat modeling of facial thermal imagery, several vital signs can be extracted, including localized blood perfusion, cardiac pulse, breath rate, and sudomotor response, since all these parameters impact the cutaneous temperature. The obtained physiological information could then be used to draw inferences about a variety of psychophysiological or affective states, as proved by the increasing number of psychophysiological studies using thermal infrared imaging. This paper presents therefore a review of the principal achievements of thermal infrared imaging in computational physiology with regard to its capability of monitoring psychophysiological activity.