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This study aims to examine how two levels of cognitive reserve, as evidenced by reading syntactic skill, modify performance and neural activity in a two-load-level (high vs. low) working memory (WM) task. Two groups of participants with different reading skills, high and low, were obtained from clustering analysis. We collected the P300 event-related potential component during the performance of the WM Sternberg task. The high reading performance (HRP) group showed a higher percentage of correct answers than the low reading performance (LRP) group in the negative probes of the WM task, which were probe stimuli not included in the memory set presented immediately before. Both groups showed P300 amplitude modulations, that is, larger WM-related P300 amplitudes for low than for high WM loads. Following the behavioral results, the HRP group displayed smaller WM-related amplitude modulations than the LRP group in the negative probes. The findings together suggest that higher levels of reading skill are associated with improved neural efficiency, which reflects in a better working memory performance.