Prior knowledge of relational structure allows people toquickly make sense of and respond to new experiences. Whenawareness of such structure is not necessary to support learn-ing, however, it is unclear when and why individuals “spon-taneously discover” an underlying relational schema. Thepresent study examines the determinants of such discovery indiscrimination-based transitive inference (TI), whereby peo-ple learn about a hierarchy of interrelated premises and aretested on their ability to draw inferences that bridge studiedassociations. Experiencing “chained” sequences of overlap-ping premises during training was predicted to facilitate thediscovery of relational structure. Among individuals withoutprior knowledge of the hierarchy, chaining improved relationallearning and was most likely to result in explicit awareness ofthe underlying relations between items. These findings addto growing evidence that the temporal dynamics of training,including successive presentation of overlapping associations,are key to understanding spontaneous relational discovery dur-ing learning.