The current study investigated whether manipulating participants’ pre-exposure to reward and punishment affects the extent to which sensation seeking and values predict risk-taking behavior. Participants (n = 195) were randomly allocated to one of two conditions, defined by the order at which they were rewarded or punished for risk-taking behavior. Risk-taking behavior was measured in both conditions using the Balloon Analogue Risk Test, but it was set up such that participants in Group 1 were rewarded for risk-taking behavior before being punished, whereas participants in Group 2 were punished for risk-taking behavior before being rewarded. Participants also completed questionnaires designed to measure sensation seeking and the values of stimulation (the need for novelty and excitement) and hedonism (the need for sensuous pleasure). It was found that stimulation predicted risk-taking behavior in the reward-then-punishment condition, whereas hedonism predicted risk-taking behavior in the punishment-then-reward condition. Sensation seeking was found to be an indirect predictor of risk-taking behavior in both conditions. It is tentatively concluded that the extent to which participants’ risk-taking behavior is guided by their values (hedonism, stimulation) largely depends on their prior exposure to the order of contingent reward and punishment.