Accurate assessment of pain by health-care professionals is essential to ensure optimal management of pain. An under-researched area is whether personality characteristics affect perception of pain in others. The aims were (a) to determine whether individual differences are associated with participants’ ability to assess pain, and (b) to determine facial cues used in the assessment of pain. One hundred and twenty-eight undergraduate students participated. They completed questionnaire assessments of empathy, pain catastrophizing, sensory sensitivity and emotional intelligence. They then viewed and rated four adult facial images (no, medium, and high pain—12 images total) using a 0–10 numerical rating scale, and noted the reasons for their ratings. (a) Empathy was the only characteristic associated with accuracy of pain assessment. (b) Descriptions of eyes and mouth, and eyes alone were most commonly associated with assessment accuracy. This was the case despite variations in the expression of pain in the four faces. Future studies could evaluate the effect on accuracy of pain assessment of (a) training empathic skills for pain assessment, and (b) emphasizing attention to the eyes, and eyes and mouth.