Emotional visual stimuli presented in laboratory settings reliably elicit prototypical patterns of subjective and psychophysiological responses. These responses likely serve distinct functions and reflect the engagement of appetitive and defensive motivational systems, making them a valuable tool for examining emotional processing in both healthy individuals and those with mental disorders. Event-related potentials (ERPs), such as the Cue-P300, Stimulus Preceding Negativity (SPN), and Late Positive Potential (LPP), provide valuable temporal insight into anticipatory and elaborative stages of emotional processing. While these components have been extensively studied using the International Affective Picture System (IAPS), concerns about its dated content have prompted the development of alternative image sets, such as the Open Affective Standardized Image Set (OASIS). Yet, ERP responses to OASIS images remain underexplored. This study aimed to compare psychophysiological and subjective responses elicited by images from the IAPS and OASIS databases, matched for valence and arousal. Twenty-two participants completed two emotional S1–S2 tasks—one using IAPS images and the other using OASIS images—while undergoing EEG recording. In each task, a cue (S1) predicted the valence (pleasant, neutral, unpleasant) of an upcoming emotional image (S2). The SPN, Cue-P300 and the LPP components were analyzed. Results revealed that unpleasant OASIS images elicited larger Cue-P300 amplitudes than unpleasant IAPS images, and both pleasant and unpleasant OASIS images evoked greater SPN amplitudes compared to their IAPS counterparts. Conversely, only IAPS images produced a robust LPP modulation, with significantly larger amplitudes for emotional versus neutral stimuli; this pattern was not observed for OASIS images. Taken together, these findings highlight the importance of stimulus selection in studies investigating emotional processing, suggesting that OASIS images may be particularly well-suited for investigating anticipatory mechanisms, whereas IAPS images remain more effective for examining affective elaboration.