The present study aimed at clarifying the precise role of pain catastrophizing, pain-related fear and personality dimensions in vigilance to pain and pain severity by means of structural equation modelling. A questionnaire survey was conducted in 122 patients with chronic or recurrent low back pain. Results revealed that pain catastrophizing and pain-related fear mediated the relationship between neuroticism and vigilance to pain. Furthermore, vigilance to pain was found to be associated with heightened pain severity. Finally, we found that neuroticism moderated the relationship between pain severity and catastrophic thinking about pain. The results strongly support the idea that vigilance to pain is dependent upon catastrophic thinking and pain-related fear. Neuroticism is best conceived of as a vulnerability factor; it lowers the threshold at which pain is perceived as threatening, and at which catastrophic thoughts about pain emerge.