The error-related negativity (ERN) is a negative deflection in the electroencephalography (EEG) waveform at frontal-central scalp sites that occurs after error commission. The relationship between the ERN and broader patterns of brain activity measured across the entire scalp that support error processing during early childhood is unclear. We examined the relationship between the ERN and EEG microstates – whole-brain patterns of dynamically evolving scalp potential topographies that reflect periods of synchronized neural activity – during both a go/no-go task and resting-state in 90, 4–8-year-old children. The mean amplitude of the ERN was quantified during the − 64 to 108 millisecond (ms) period of time relative to error commission, which was determined by data-driven microstate segmentation of error-related activity. We found that greater magnitude of the ERN associated with greater global explained variance (GEV; i.e., the percentage of total variance in the data explained by a given microstate) of an error-related microstate observed during the same − 64 to 108 ms period (i.e., error-related microstate 3), and to greater parent-report-measured anxiety risk. During resting-state, six data-driven microstates were identified. Both greater magnitude of the ERN and greater GEV values of error-related microstate 3 associated with greater GEV values of resting-state microstate 4, which showed a frontal-central scalp topography. Source localization results revealed overlap between the underlying neural generators of error-related microstate 3 and resting-state microstate 4 and canonical brain networks (e.g., ventral attention) known to support the higher-order cognitive processes involved in error processing. Taken together, our results clarify how individual differences in error-related and intrinsic brain activity are related and enhance our understanding of developing brain network function and organization supporting error processing during early childhood.