People are more and more using social networking sites (SNSs) like Facebook and MySpace to engage with others. The use of SNSs can have both positive and negative effect on the individual; however, the increasing use of SNSs might reveal that people look for SNSs because they have a positive experience when they use them. Few studies have tried to identify which particular aspects of the social networking experience make SNSs so successful. In this study we focus on the affective experience evoked by SNSs. In particular, we explore whether the use of SNSs elicits a specific psychophysiological pattern. Specifically, we recorded skin conductance, blood volume pulse, electroencephalogram, electromyography, respiratory activity, and pupil dilation in 30 healthy subjects during a 3-minute exposure to (a) a slide show of natural panoramas (relaxation condition), (b) the subject's personal Facebook account, and (c) a Stroop and mathematical task (stress condition). Statistical analysis of the psychophysiological data and pupil dilation indicates that the Facebook experience was significantly different from stress and relaxation on many linear and spectral indices of somatic activity. Moreover, the biological signals revealed that Facebook use can evoke a psychophysiological state characterized by high positive valence and high arousal (Core Flow State). These findings support the hypothesis that the successful spread of SNSs might be associated with a specific positive affective state experienced by users when they use their SNSs account.