Introduction: This study investigated the time course of attention to pain and examined the moderating effect of attentional control in the relationship between pain catastrophizing and attentional bias in chronic pain patients. Methods: A total of 28 patients with chronic pain and 29 pain-free individuals observed pictures of pain, happy and neutral facial expressions while their gaze behaviour was recorded. Pain intensity and duration, anxiety, depression, stress, attentional control and pain catastrophizing were assessed by questionnaires. Results: In all subjects, the pattern of attention for pain faces was characterized by initial vigilance, followed by avoidance. No significant difference was found between the two groups in terms of orientation towards the stimuli, the duration of first fixation, the average duration of fixation or number of fixations on the pain stimuli. Attentional control moderated the relationship between catastrophizing and overall dwell time for happy faces in pain patients, indicating that those with high attentional control and high catastrophizing focused more on happy faces, whereas the reverse was true for those with low attentional control. Conclusion: This study supported the vigilance–avoidance pattern of attention to painful facial expressions and a moderation effect of attentional control in the association between pain catastrophizing and attentional bias to happy faces among pain patients.