Positive and negative consequences of using social media (SM) have been observed. Excessive use of SM, such as Facebook, can lead to problematic behaviours, resulting in emotional and social functioning changes. Moreover, the problematic use of SM is negatively associated with empathy’s affective and cognitive components. The present study used functional near-infrared spectroscopy (fNIRS) to test empathy differences between problematic and non-problematic Facebook users. In addition, the Facebook-related context that may modulate empathic response was investigated. Fifty-two participants (25 females; Mage = 24.6 years [SD ± 2.9]) took part in the study and were classified into two groups: non-problematic and problematic Facebook users. The study was conducted using the empathy for pain paradigm with three media-related contextual conditions: newspaper, Facebook-related, and neutral. The results indicated there was a statistically significant difference between the left and right side of the prefrontal cortex (PFC) among nonproblematic Facebook users when observing pain stimuli in the context of Facebook. For problematic Facebook users, there was significantly more activity on the left side of the PFC (compared to the right side) when observing painful stimuli in the newspaper context and non-painful stimuli in a neutral context. The differences in haemodynamic activity registered by fNIRS between the left and right PFCs were observed in both groups and may have resulted from difficulties in regulating emotional response and attention, particularly among the problematic Facebook user group.