Empathy for pain is at the basis of altruistic behaviors and is known to be modulated by variables such as group membership, pleasantness or unpleasantness of situations and social relationships. Also, face attractiveness and aesthetic judgment might play a role when observing a person in painful conditions, by increasing individuals\' empathic responsiveness. Indeed, physical attractiveness can modify both the perception of the face itself and its reception in a social context. In the present study, we aimed to assess cortical activity when attention is focused on the aesthetic features of an individual showing painful feelings. Brain activity (optical imaging: functional near-infrared spectroscopy, fNIRS), considered in its hemodynamic components (oxygenated [oxy-Hb] and deoxygenated hemoglobin [deoxy-Hb]) was monitored when 22 subjects (Mage = 24.9; SD = 3.6) observed faces (attractive; unattractive) that received painful stimulations (pain; no pain) and were asked to judge the attractiveness and pain condition of the face. Specifically, we targeted the left and right inferior frontal gyrus (IFG), sensory cortex, and temporo-parietal junction (TPJ). Analyses revealed significant lower oxy-Hb levels in left IFG compared to right hemispheric channels when asking participants to rate faces attractiveness independently from the stimulus features. Besides, lower levels of deoxy-Hb were detected in the right TPJ for unattractive faces compared to attractive faces. Overall, present findings highlighted that the formulation of an aesthetic judgment and face attractiveness plays a relevant role in empathic concerns and this seems to be able to overlay painful appraisal.