This study investigated age differences in appetitive and aversive associative learning using a Pavlovian conditioning paradigm. Appetitive and aversive associative learning is the process by which an initially neutral cue is systematically paired with an aversive or appetitive outcome, eventually itself prompting aversive or appetitive responses. Mimicking the motivational shift from a primary gain orientation in young adulthood toward a stronger orientation toward loss prevention in old age, we expected older adults to learn associations between novel stimuli and losses more rapidly than associating neutral cues with gains (here: donations to charity). A pilot study (N = 214, 18–81 years) established the equivalence of monetary gains and losses for a charitable donation across adulthood. Based on these data, an experiment using an associative conditioning paradigm assessed the extent and temporal dynamics of appetitive and aversive learning across adulthood (N = 122, 19–80 years). Results suggest that younger adults form gain-related associations at a higher learning rate compared to losses. By contrast, with increasing age, adults more rapidly track the valence of conditioned stimuli with losses than gains. This differential learning pattern cannot be attributed to age-differences in arousal or expectancy. Results suggest that the negative valence of losses drives learning more efficiently in older age groups, while younger age groups are more sensitive to the positive valence of gains.