The motivation to strive for and consume primary rewards such as palatable food is bound by devaluation mechanisms, yet secondary rewards such as money may not be bound by these regulatory mechanisms. The present study therefore aimed at determining diverging devaluation trajectories for primary (chocolate milk) and secondary (money) reinforcers on the behavioral and neural level. Devaluation procedures with repeated exposure to reward combined with a choice (Experiment 1) and an incentive delay (Experiment 2) paradigm consistently revealed decreasing hedonic value for the primary reward as reflected by decreasing hedonic evaluation and choice preference with repeated receipt, while hedonic value and preferences for the secondary reward increased. Concomitantly acquired functional near-infrared spectroscopy (fNIRS) data during the incentive delay paradigm revealed that increasing value of the secondary reward was accompanied by increasing anticipatory activation in the lateral orbitofrontal cortex, while during the consummatory phase the secondary reinforcer associated with higher medial orbitofrontal activity irrespective of devaluation stage. Overall, the findings suggest that-in contrast to primary reinforcers-secondary reinforcers, i.e. money, can acquire progressively enhanced incentive motivation with repeated receipt, suggesting a mechanism which could promote escalating striving to obtain secondary rewards.