ERP responses to spoken words are sensitive to both rhyming effects and effects of associated spelling patterns. Are such effects automatically elicited by spoken words or dependent on selectively attending to phonology? To address this question, ERP responses to spoken word pairs were investigated under two equally demanding listening tasks that directed selective attention either to sub-syllabic phonology (i.e., rhyme judgments) or to melodies embedded within the words. ERPs elicited when participants selectively attended to phonology demonstrated a rhyming effect that was concurrent with online stimulus encoding and an orthographic effect that emerged later. ERP responses to the same stimuli presented under melodic focus, however, showed no evidence of sensitivity to rhyme or spelling patterns. Results reveal limitations to the automaticity of such ERP effects, suggesting that rhyme effects may depend, at least to some degree, on allocation of attention to phonology, which may in turn activate task-incidental orthographic information.