Executive functioning (EF) and motivation are associated with academic achievement and error-related ERPs. The present study explores whether early academic skills predict variability in the error-related negativity (ERN) and error positivity (Pe). Data from 113 three- to seven-year-old children in a Go/No-Go task revealed that stronger early reading and math skills predicted a larger Pe. Closer examination revealed that this relation was quadratic and significant for children performing at or near grade level, but not significant for above-average achievers. Early academics did not predict the ERN. These findings suggest that the Pe – which reflects individual differences in motivational processes as well as attention – may be associated with early academic achievement.