Extraversion has been shown to positively correlate with activation within the ventral striatum, amygdala and other dopaminergically innervated, reward-sensitive regions. These regions are implicated in emotional responding, in a manner sensitive to attentional focus. However, no study has investigated the interaction among extraversion, emotion and attention. We used fMRI and dynamic, evocative film clips to elicit amusement and sadness in a sample of 28 women. Participants were instructed either to respond naturally (n = 14) or to attend to and continuously rate their emotions (n = 14) while watching the films. Contrary to expectations, striatal response was negatively associated with extraversion during amusement, regardless of attention. A negative association was also observed during sad films, but only when attending to emotion. These findings suggest that attentional focus does not influence the relationship between extraversion and neural response to positive (amusing) stimuli but does impact the response to negative (sad) stimuli.