Pavlovian aversive conditioning is a fundamental form of learning helping organisms survive in their environment. Previous research has suggested that organisms are prepared to preferentially learn to fear stimuli that have posed threats to survival across evolution. Here, we examined whether enhanced Pavlovian aversive conditioning can occur to stimuli that are relevant to the organism's concerns beyond biological and evolutionary considerations, and whether such preferential learning is modulated by inter-individual differences in affect and motivation. Seventy-two human participants performed a spatial cueing task where the goal-relevance of initially neutral stimuli was experimentally manipulated. They subsequently underwent a differential Pavlovian aversive conditioning paradigm, in which the goal-relevant and goal-irrelevant stimuli served as conditioned stimuli. Skin conductance response was recorded as an index of the conditioned response and participants' achievement motivation was measured to examine its impact thereon. Results show that achievement motivation modulated Pavlovian aversive learning to goal-relevant vs. goal-irrelevant stimuli. Participants with high achievement motivation more readily acquired a conditioned response to goal-relevant compared with goal-irrelevant stimuli than did participants with lower achievement motivation. However, no difference was found between goal-relevant and goal-irrelevant stimuli during extinction. These findings suggest that stimuli that are detected as relevant to the organism can induce facilitated Pavlovian aversive conditioning even though they hold no inherent threat value and no biological evolutionary significance, and that the occurrence of such learning bias is critically dependent on inter-individual differences in the organism's concerns, such as achievement motivation.