Learning the contingencies between a situational context (S), one's own responses (R), and their outcomes (O) and selecting responses according to their anticipated outcomes is the basis of a goal-directed behavior. Previous imaging studies found the angular gyrus (AG) to be correlated to both the representation of R-O associations and outcome-based response selection. Based on this correlational relationship, we investigated the causal link between AG function and goal-directed behavior in offline and online TMS experiments. To this end, we employed an experimental R-O compatibility paradigm testing outcome anticipation during response selection and S-R-O knowledge to probe S-R-O learning. In Experiment 1, we applied 1-Hz rTMS offline to the AG or the vertex before participants performed the experimental tasks. In Experiment 2, we applied online 10-Hz pulse trains to the AG or used sham stimulation during an early action selection stage in half of the trials. In both experiments, the R-O compatibility effect was unaltered when response selection was outcome-based, suggesting no causal role of the AG in outcome anticipation during response selection. However, in both experiments, groups with AG stimulation showed significantly modulated knowledge of S-R-O associations in a posttest. Additionally, in an explorative analysis, we found an induced R-O compatibility effect later in the experiment when response selection was guided by stimulus–response rules, suggesting reduced selectivity of outcome anticipation. We discuss possible compensatory behavioral and brain mechanism as well as specific TMS-related methodical considerations demonstrating important implications for further studies investigating cognitive function by means of TMS.