Adults of varying reading comprehension skill learned a set of previously unknown rare English words (e.g., gloaming) in three different learning conditions in which the type of word knowledge was manipulated. The words were presented in one of three conditions: (1) orthography-to-meaning (no phonology); (2) orthography-to-phonology (no meaning); and (3) phonology-to-meaning (no orthography). Following learning, participants made meaning judgments on the learned words, familiar known words, and unpresented (unlearned) rare words while their ERPs were recorded. The behavioral results showed no significant effects of comprehension skill on meaning judgment performance. Contrastingly, the ERP results indicated comprehension skill differences in P600 amplitude; high-skilled readers showed stronger familiarity effects for learned words, whereas less-skilled readers did not distinguish between learned words, familiar words, and unlearned words. Evidence from the P600 and N400 illustrated superior learning of meaning when meaning information was coupled with orthography rather than phonology. These results suggest that the availability of word knowledge (orthography, phonology, and meaning) at learning affects subsequent word identification processes when the words are encountered in a new context.