Past research showed that social networking sites represent perfect platforms to satisfy narcissistic needs. The present study aimed to investigate how grandiose (GN) and vulnerable narcissism (VN) as well as social comparisons are associated with Facebook activity, which was measured with a self-report on three activity dimensions: Acting, Impressing, and Watching. In addition, the state self-esteem (SSE) was measured with respect to performance, social behavior, and appearance. One hundred and ten participants completed an online survey containing measures of SSE and Facebook activity and a priming procedure with three experimental conditions embedded in a social media context (upward comparison, downward comparison, and control group). Results indicated, as expected, that high VN was negatively associated with SSE on each subscale and the overall score. In addition, it was found that VN, but not GN, displayed positive associations with frequency of Facebook activities. Finally, it was proposed and confirmed that VN in interaction with the priming of downward comparisons negatively affected SSE. The conclusion drawn is that VN represents a key variable for the prediction of self-esteem as well as for the frequency of Facebook activity.