Learning the acoustic and phonological information in lexical tones is significant for learners of tonal languages. Although there is a wealth of knowledge from studies of second language (L2) tone learning, it remains unclear how L2 learners process acoustic versus phonological information differently depending on whether their first language (L1) is a tonal language. In the present study, we first examined proficient L2 learners of Mandarin with tonal and nontonal L1 in a behavioral experiment (identifying a Mandarin tonal continuum) to construct tonal contrasts that could differentiate the phonological from the acoustic information in Mandarin lexical tones for the L2 learners. We then conducted an ERP experiment to investigate these learners’ automatic processing of acoustic and phonological information in Mandarin lexical tones by mismatch negativity (MMN). Although both groups of L2 learners showed similar behavioral identification features for the Mandarin tonal continuum as native speakers, L2 learners with nontonal L1, as compared with both native speakers and L2 learners with tonal L1, showed longer reaction time to the tokens of the Mandarin tonal continuum. More importantly, the MMN data further revealed distinct roles of acoustic and phonological information on the automatic processing of L2 lexical tones between the two groups of L2 learners. Taken together, the results indicate that the processing of acoustic and phonological information in L2 lexical tones may be modulated by L1 experience with a tonal language. The theoretical implications of the current study are discussed in light of models of L2 speech learning.