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Neural markers of attention, including those frequently linked to the event-related potential P3 (P300) or P3b component, vary widely within and across participants. Understanding the neural mechanisms of attention that contribute to the P3 is crucial for better understanding attention-related brain disorders. All ten participants were scanned twice with a resting-state PCASL perfusion MRI and an ERP with a visual oddball task to measure brain resting-state functional connectivity (rsFC) and P3 parameters (P3 amplitudes and P3 latencies). Global rsFC (average rsFC across the entire brain) was associated with both P3 amplitudes (r = 0.57, p = 0.011) and P3 onset latencies (r = −0.56, p = 0.012). The observed P3 parameters were correlated with predicted P3 amplitude from the global rsFC (amplitude: r = +0.48, p = 0.037; latency: r = +0.40, p = 0.088) but not correlated with the rsFC over the most significant individual edge. P3 onset latency was primarily related to long-range connections between the prefrontal and parietal/limbic regions, while P3 amplitudes were related to connections between prefrontal and parietal/occipital, between sensorimotor and subcortical, and between limbic/subcortical and parietal/occipital regions. These results demonstrated the power of resting-state PCASL and P3 correlation with brain global functional connectivity.