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Previous studies have consistently shown that repeated exposure to emotional stimuli leads to a reduction in cortical and autonomic responses (affective habituation). These findings emerge from studies conducted within a single experimental session, preventing the possibility of disentangling short‐term from long‐term habituation effects. The present study investigated whether affective habituation reflects a short‐living learning process, or a more stable change involving long‐term memory. Participants went through a first habituation phase consisting of 80 repetitions of the same set of emotional and neutral pictures, when event‐related potentials and oscillatory activity were measured (Session 1). Crucially, after a 1‐day interval, the same participants were exposed to a second habituation phase with the same stimuli that had been seen before. Results showed that the attenuation of the late positive potential (LPP) affective modulation prompted throughout repetitions of Session 1 remained unchanged after a 1‐day interval, and this between‐session habituation effect, which was specific to repeated exemplars, was consistent across different emotional contents. Alpha desynchronization was clearly enhanced for pictures of erotica and mutilation and this modulatory pattern remained fairly stable over repetitions. Altogether, these findings suggest that LPP affective habituation is not a short‐living learning process, but, rather, reflects a strengthened long‐term memory representation of specific repeated stimuli.