The current study examined whether an important temperamental characteristic, effortful control (EC), moderates the associations between dispositional anger and sadness, attention biases, and social functioning in a group of preschool-aged children (N = 77). Preschoolers’ attentional biases toward angry and sad facial expressions were assessed using eye-tracking, and we obtained teachers’ reports of children’s temperament and social functioning. Associations of dispositional anger and sadness with time looking at relevant negative emotional stimuli were moderated by children’s EC, but relations between time looking at emotional faces and indicators of social functioning, for the most part, were direct and not moderated by EC. In particular, time looking at angry faces (and low EC) predicted high levels of aggressive behaviors, whereas longer time looking at sad faces (and high EC) predicted higher social competence. Finally, latency to detect angry faces predicted aggressive behavior under conditions of average and low levels of EC. Findings are discussed in terms of the importance of differentiating between components of attention biases toward distinct negative emotions, and implications for attention training.