Social networks, particularly those defined by friendships, influence many childhood and adolescent health behaviors such as the use of alcohol, tobacco, and other drugs, as well as diet and physical activity. Few, if any, studies have examined the concordance between friendship networks and sun exposure/safety behaviors. This study examines the friendship networks and sun safety behaviors for a group of fourth and fifth grade students taking part in a larger sun safety intervention, “SunSmart” (n = 128). Intra-class correlation, homophily hypothesis testing, and exponential random graph models were used to test friendship homophily based on sun safety behaviors. Peer Leaders were identified through social network popularity, and sun safety change scores were compared between Peer Leaders and non-leaders. Results show that students cluster based on shared demographic characteristics and some sun safety behaviors, and that there was a trend for Peer Leaders to respond better to the SunSmart intervention than non-leaders. Implications for future sun safety interventions using Peer Leaders as champions for sun safety behavior change are discussed.