High shyness during early adolescence is associated with impaired peer relationships and risk for psychiatric disorders. Little is known, however, about the relation between shyness and trajectories of brain development over early adolescence. The current study longitudinally examined trajectories of resting-state functional connectivity (rs-fc) within four brain networks in 147 adolescents. Subjects underwent functional magnetic resonance imaging at three different time points, at average ages 10.5 (range = 7.8–13.0), 11.7 (range = 9.3–14.1), and 12.9 years (range = 10.1–15.2). Multilevel linear modeling indicated that high shyness was associated with a less steep negative slope of default mode network (DMN) rs-fc over early adolescence relative to low shyness. Less steep decreases in DMN rs-fc may relate to increased self-focus in adolescents with high shyness.