Social learning can help individuals to efficiently acquire knowledge and skills. In the classroom, social learning often takes place in structured settings in which peers help, support, and tutor each other. Several protocols have been developed to make peer-assisted learning (PAL) more efficient. However, little attention has been devoted to how the transfer of knowledge is shaped by the social relationship between peers, and their relative positions in the social network. To address this gap, we combined social network analysis with an experimental social learning task, in which pupils (N = 135; aged 11-19) could use social information from their peers to improve their performance. We show that pupils' tendencies to use social information substantially decrease with the peer's distance in the social network. This effect is mediated by subjective closeness: pupils report feeling much closer to their friends than to their non-friends, and closeness strongly enhances social learning. Our results further show that, above and beyond these effects of network distance, social information use increases with the peer's social status (network centrality) and perceived smartness. Our results provide empirical evidence in a naturalistic setting for the role of specific network attributes in shaping pupils' willingness to learn from their peers. These findings illustrate the value of a social network approach for understanding knowledge transfer in the classroom and can be used to structure more effective peer learning.