Pavlovian and instrumental conditioning are fundamental processes helping organisms learn about stimuli that predict rewards in the environment and actions that lead to their obtainment. These two forms of learning and their interplay notably exert a strong impact on reward-seeking behaviors. Here, we examined in humans whether Pavlovian and instrumental learning along with their effects on cue-driven behaviors involving sexual rewards are modulated by the reward relevance to the individual's sexual orientation. In two experiments, we manipulated the concern-relevance of sexual outcomes in a Pavlovian-instrumental transfer paradigm by recruiting heterosexual and homosexual men and selecting sexual stimuli for each sexual orientation. Results showed enhanced instrumental and Pavlovian learning in response to the most relevant sexual outcome to participants' sexual orientation as well as increased reward-seeking behaviors in response to its associated cue compared to the less relevant sexual outcome and its associated cue, respectively, thereby reflecting that inter-individual differences in sexual concerns modulated these effects. These findings suggest that motivational influence on reward-related learning and behaviors involving sexual stimuli relies on inter-individual differences in concerns and contribute to fostering further insight into the mechanisms underlying human reward-seeking behaviors.