How daily physical activity and sedentary time relate to human judgement and functional connectivity (FC) patterns that support them remains underexplored. We investigated the relationships between accelerometer-measured moderate-to-vigorous physical activity (MVPA) and sedentary time to decision-making competence (DMC) in young adults using a comprehensive Adult-Decision Making Competence battery. We applied graph theory measures of global and local efficiency to test the mediating effects of FC in cognitively salient brain networks (fronto-parietal; dorsal attention, DAN; ventral attention; and default mode), assessed from the resting-state fMRI. Sedentary time was related to lower susceptibility to a framing bias. However, once global and local efficiency of the DAN were considered we observed (1) higher susceptibility to framing with more sedentary time, mediated through lower local and global efficiency in the DAN, and (2) lower susceptibility to framing with more sedentary time. MVPA was not related to DMC or graph theory measures. These results suggest that remaining sedentary may reduce neurofunctional readiness for top-down control and decrease engagement of deliberate thought, required to ignore irrelevant aspects of a problem. The positive effect suggests that the relationship between sedentary time and DMC may be moderated by unmeasured factors such as the type of sedentary behavior.