Abstract Most words in a language have more than one meaning. Yet, few studies have explicitly examined the acquisition of secondary meanings of L2 words and the extent to which polysemy and homonymy affect vocabulary learning. This study explores the effect of polysemy and homonymy on the deliberate acquisition of the form–meaning connections of L2 words. Thirty-six EFL learners (compared with a control group of 30) learned secondary polysemous and homonymous meanings of familiar words and primary meanings of unfamiliar words using flashcards. Knowledge of target words was measured using meaning–recall and meaning–recognition tests immediately after the treatment and again one week later. The findings indicated that learning another meaning for a familiar word was just as difficult as learning the primary meaning of an unfamiliar word, suggesting that the type of meaning (primary, secondary polysemous, or secondary homonymous) might not be an influencing factor in the deliberate acquisition of L2 words.