Second-order conditioning (SOC; i.e., conditioned responding to S2 as a result of S1-US pairings followed by S2-S1 pairings) is generally explained by either a direct S2→US association or by an associative chain (i.e., S2→S1→US). Previous research found that differences in responses to S2 after S1 was extinguished often depended on the nature of the S2-S1 pairings (i.e., sequential or simultaneous). In two experiments with human participants, we examined the possibility that such differences result from S1 evoking S2 during extinction of S1 following simultaneous but not sequential S2-S1 pairings. This evocation of S2 by S1 following simultaneous pairings may have paired the evoked representation of S2 with absence of the outcome, thereby facilitating mediated extinction of S2. Using sequential S2-S1 pairings, both Experiments 1 and 2 failed to support this account of how extinction of S1 reduced responding to S2. Experiment 1 found that extinguishing S1 reduced responding to S2, while extinguishing S2 had little effect on responses to S1, although forward evocation of S1 during extinction of S2 paired the evoked representation of S1 with absence of the outcome. In Experiment 2, evocation of S2 during S1 nonreinforced trials was prevented because S2-S1 pairings followed (rather than proceeded) S1-alone exposures. Nevertheless, responding to S2 at test mimicked S1 responding. Responding to S2 was high in the context in which S1 had been reinforced and low in the context in which S1 had been nonreinforced. Collectively, these experiments provide additional support for the associative-chain account of SOC.