Prior research suggests that nonpredictive symbolic central cues can produce nonvoluntary shifts of endogenous attention when associations between cues and spatial locations are overlearned during cognitive development. The present ERP study extends this research by first showing that overlearned cue–spatial location associations necessary to support nonvoluntary attentional orienting can be rapidly formed in adult humans. A second experiment indicates that the nonvoluntary orienting formed by such rapid learning is semireflexive (amenable to top-down influence) rather than reflexive (resistant to top-down influence). A third experiment suggests that the rapid formation of endogenous nonvoluntary orienting requires explicit rather than implicit learning of cue–location associations. These findings provide further support for a strong connection between neurocognitive representations of space, symbol meaning, and attentional control.