Although the P3b component of the event‐related brain potential is one of the most widely studied components, its underlying generators are not currently well understood. Recent theories have suggested that the P3b is triggered by phasic activation of the locus‐coeruleus norepinephrine (LC‐NE) system, an important control center implicated in facilitating optimal task‐relevant behavior. Previous research has reported strong correlations between pupil dilation and LC activity, suggesting that pupil diameter is a useful indicator for ongoing LC‐NE activity. Given the strong relationship between LC activity and pupil dilation, if the P3b is driven by phasic LC activity, there should be a robust trial‐to‐trial relationship with the phasic pupillary dilation response (PDR). However, previous work examining relationships between concurrently recorded pupillary and P3b responses has not supported this. One possibility is that the relationship between the measures might be carried primarily by either inter‐individual (i.e., between‐participant) or intra‐individual (i.e., within‐participant) contributions to coupling, and prior work has not systematically delineated these relationships. Doing so in the current study, we do not find evidence for either inter‐individual or intra‐individual relationships between the PDR and P3b responses. However, baseline pupil dilation did predict the P3b. Interestingly, both the PDR and P3b independently predicted inter‐individual and intra‐individual variability in decision response time. Implications for the LC‐P3b hypothesis are discussed.