People seem to have difficulties when perceiving events whose outcome has no influence on the outcome of future events. This illusion that patterns exist where there are none may lead to adverse consequences, such as escalating losses in financial trading or gambling debt. Despite the enormous social consequences of these cognitive biases, however, their neural underpinnings are poorly understood. Attempts to investigate them have so far relied on evoked neural activity, whereas spontaneous brain activity has been treated as noise to be averaged out. Here, we focus on the spontaneous electroencephalographic (EEG) activity during inter-trial-intervals (ITI) in a sequential risky decision-making task. Using multilevel mediation analyses, our results show that the percentage of time covered by two EEG microstates (i.e., functional brain-states of coherent activity) mediate the influence of outcomes of prior decisions on subsequent risk taking on a trial-by-trial basis. The devised multilevel mediation analysis of the temporal characteristics of EEG microstates during ITI provides a new window into the neurobiology of decision making by bringing the spontaneous brain activity to the forefront of the analysis.