Rapid and accurate perception of faces is a necessary human skill. We have the ability to quickly perceive and identify individual faces in different visual contexts. We can also recall complex knowledge about those faces, such as their social relationships with others, but the precise timing of this process has not been examined. This study addressed these questions through the utilization of electroencephalography (EEG) and representational similarity analysis (RSA). In Experiment 1, participants became familiar with a 10-person social network, and were then shown faces within that network while EEG was recorded. The similarity structure of neural patterns in response to these faces was compared with models of visual, identity, and social closeness, to understand the temporal dynamics of the cognitive processes related to face perception. Visual models became significant early after onset, and social closeness was significant starting after 200 ms. The identity model also became significant early and stayed associated with neural patterns until after the social closeness model's association. In Experiment 2, participants viewed the same faces and were directed to either attend to the friendships of the faces seen (social condition), or physical locations related to the faces (non-social condition). Social and non-social conditions were compared to assess whether social network relationship information present in the brain is attention-dependent. Visual similarity, face space, and identity representations again became significant early after face onset. The face space model stayed significant longer in the location attention condition, suggesting that visual properties of a face are used to remember past locations. In the social attention condition, the identity model remained significant longer, suggesting that identity is closely tied to social information, but not necessarily location information. A model of social closeness restricted to the strongest relationships also showed early associations with neural pattern similarity. This model was significant in both attention conditions, although it remained more strongly associated with neural patterns later in the social condition. These findings indicate that information about social network relationships is accessed shortly following the visual perception of faces, and is spontaneously produced even in the absence of explicit attention to the relationships, but explicit social attention causes these representations to be sustained longer. This data supports the proposal that information about social connections is closely linked to representations of face identity and is produced partially independent of task demands, suggesting that non-visual social information is particularly relevant to people during social perception.