Observers’ psychological characteristics can influence the way in which they perceive pain in others. The goal of this study was to examine if observers’ sensitivity and accuracy in perceiving others’ emotions during pain can be explained by their level of pain catastrophizing or neuroticism. Participants were 87 undergraduate students who completed the pain catastrophizing scale (PCS) and the neuroticism subscale of the Big Five Inventory (nBFI). Upon completion, participants watched videos of individuals experiencing pain during a laboratory pain induction task and provided ratings concerning pain and emotions expressed on the videos. A comparison was made between observers’ ratings and self-report pain ratings of target individuals in the videos. The results indicated that participants who scored higher on the PCS provided more accurate pain ratings only when the target individual in the pain videos also scored high on the PCS. Similarly, participants who scored higher on the PCS or the nBFI did not perceive others’ pain as being more severe, compared to participants with lower PCS and nBFI scores. Subsequent analyses indicated that observers who scored high on the PCS perceived more facial expressions of anger and fear during pain. Nonetheless, comparison with objective coding of the facial expressions of the target individuals showed they did not perceive these emotions more accurately than those with lower PCS scores. That is, they perceived anger and fear that were not expressed when considering facial action coding as the gold standard. There were no sex differences in observers’ perceptions.