Facebook is a platform for social contacts, establishing relationships, and solving interpersonal conflicts. Consequently, understanding online emotional and social behaviour in problematic and nonproblematic Facebook use is important to explore how people function on social media. In this context, the current study examined the differences between participants with low (LPFU) and high (HPFU) problematic Facebook use in pain perception associated with empathic processes using the event-related potential (ERP) paradigm. More precisely, the current study verified the impact of problematic Facebook use on pain-related stimuli during a subliminal affective priming paradigm task. Three types of priming were used: Facebook-related, pain-related, and neutral. The results showed that the HPFU group answered more slowly than the individuals from LPFU. Ad- ditionally, the N2 amplitude was sensitive both for Facebook-related and pain-related primes and painful and nonpainful stimuli types in the HPFU and LPFU groups. However, for the HPFU group, the N2 amplitude was more negative in the painful stimulus condition than in the nonpainful stim- ulus condition in the Facebook-related prime. The findings also showed that the P3 component was more positive in nonpainful than painful conditions. The study's results allow us to better un- derstand the functioning of Facebook users in the context of emotional and social behavior online.