Attention selects which aspects of sensory input are brought to awareness. To promote survival and well-being, attention prioritizes stimuli both voluntarily, according to context-specific goals (e.g., searching for car keys), and involuntarily, through attentional capture driven by physical salience (e.g., looking toward a sudden noise). Valuable stimuli strongly modulate voluntary attention allocation, but there is little evidence that high-value but contextually irrelevant stimuli capture attention as a consequence of reward learning. Here we show that visual search for a salient target is slowed by the presence of an inconspicuous, task-irrelevant item that was previously associated with monetary reward during a brief training session. Thus, arbitrary and otherwise neutral stimuli imbued with value via associative learning capture attention powerfully and persistently during extinction, independently of goals and salience. Vulnerability to such value-driven attentional capture covaries across individuals with working memory capacity and trait impulsivity. This unique form of attentional capture may provide a useful model for investigating failures of cognitive control in clinical syndromes in which value assigned to stimuli conflicts with behavioral goals (e.g., addiction, obesity).