The current study examined behavioral measures and response-locked event-related brain potentials (ERPs) derived from a Go/No-Go task in a large (N = 328) sample of 5- to 7-year-olds in order to better understand the early development of response monitoring and the impact of child age and sex. In particular, the error-related negativity (ERN, defined on both error trials alone and the difference between error and correct trials, or ΔERN), correct response negativity (CRN), and error positivity (Pe) were examined. Overall, the ERN, CRN, and the Pe were spatially and temporally similar to those measured in adults and older children. Even within our narrow age range, older children were faster and more accurate; a more negative ΔERN and a more positive Pe were associated with: increasing age, increased accuracy, and faster reaction times on errors, suggesting these enhanced components reflected more efficient response monitoring of errors over development. Girls were slower and more accurate than boys, although both genders exhibited comparable ERPs. Younger children and girls were characterized by increased posterror slowing, although they did not demonstrate improved posterror accuracy. Posterror slowing was also related to a larger Pe and reduced posterror accuracy. Collectively, these data suggest that posterror slowing may be unrelated to cognitive control and may, like the Pe, reflect an orienting response to errors.