Although the semantic relationships among words have long been acknowledged as a crucial component of adult lexical knowledge, the ontogeny of lexical networks remains largely unstudied. To determine whether learners encode relationships among novel words, we trained 2-year-olds on four novel words that referred to four novel objects, which were grouped into two visually similar pairs. Participants then listened to repetitions of word pairs (in the absence of visual referents) that referred to objects that were either similar or dissimilar to each other. Toddlers listened significantly longer to word pairs referring to similar objects, which suggests that their representations of the novel words included knowledge about the similarity of the referents. A second experiment confirmed that toddlers can learn all four distinct words from the training regime, which suggests that the results from Experiment 1 reflected the successful encoding of referents. Together, these results show that toddlers encode the similarities among referents from their earliest exposures to new words.