Some stimuli can orient attentional resources and access awareness even if they appear outside the focus of voluntary attention. Stimuli with low-level perceptual salience and stimuli with an emotional content can modulate attention independently of voluntary processes. In Experiment 1, we used a spatial cuing task to investigate whether stimuli that are controlled for their perceptual salience can modulate the rapid orienting of attention based exclusively on their affective relevance. Affective relevance was manipulated through a Pavlovian conditioning paradigm in which an arbitrary and affectively neutral perceptual stimulus was associated with a primary reward (i.e., a chocolate odor). Results revealed that, after conditioning, attentional resources were rapidly oriented toward the stimulus that was previously associated with the reward. In Experiment 2, we used the very same conditioning procedure, but we devaluated the reward after conditioning for half of the participants through a sensory-specific satiation procedure. Strikingly, when the reward was devaluated, attention was no longer oriented toward reward-associated stimuli. Our findings therefore suggest that reward associations rapidly modulate visual processing independently of both voluntary processing and the perceptual salience of the stimulus. This supports the notion that stimuli associated with primary rewards modulate rapid attention orienting on the basis of the affective relevance of the stimulus.