Salivary alpha-amylase (sAA) was examined as a predictor of children's externalizing symptoms cross-sectionally when children were in the 3rd grade (T1; N=64) and again in the 5th grade (T2; N=54) and longitudinally over two years. Parasympathetic nervous system (PNS) activity, indexed by respiratory sinus arrhythmia (RSA), was examined as a moderator of the sAA and child externalizing link. Participants were healthy, typically developing children, 34% of whom were African American and the rest European American. At each time point, saliva samples were collected during afternoon laboratory visits and assayed for sAA. Children's RSA was measured during baseline conditions and in response to an inter-adult argument and a star-tracing task. Cross-sectional associations between sAA and externalizing symptoms at T1 and T2 were moderated by PNS functioning. Longitudinally, sAA was directly associated with changes in externalizing symptoms in a non-linear fashion. Specifically, lower externalizing symptoms were predicted for children with moderate levels of sAA, but higher externalizing was predicted for children with higher or lower levels of sAA. Findings highlight the importance of the contemporaneous assessment of SNS and PNS functioning in the prediction of child psychopathology, and the need to examine curvilinear relations between ANS functioning and behavior.