Impulsivity and sensation seeking are considered to be among the most important personality traits involved in risk-taking behavior. This study is focused on whether the association of these personality traits and brain functional connectivity depends on individuals' risk proneness. Risk proneness was assessed with the DOSPERT-30 scale and corroborated with performance in a motorcycle simulator. The associations of impulsivity- and sensation seeking-related traits with the between and within coupling of seven major brain functional networks, estimated from electroencefalograma (EEG) recordings, differ according to whether an individual is risk prone or not. In risk-prone individuals, (lack of) premeditation enhanced the coupling of the ventral attention and limbic networks. At the same time, emotion seeking increased the coupling of the frontoparietal network and the default mode networks (DMNs). Finally, (lack of) perseverance had a positive impact on the coupling of anterior temporal nodes of the limbic network whilst having a negative impact on some frontal nodes of the frontoparietal network and the DMNs. In general, the results suggest that the predisposition to behave riskily modulates the way in which impulsivity traits are linked to brain functionality, seemingly making the brain networks prepare for an immediate, automatic, and maladaptive response.