This study examined behavioral and neurophysiological indices of discrimination of an English vowel contrast [ɪ–ɛ] by early and late bilingual Spanish–English speakers, compared to monolingual English speakers. Electrophysiological measures (Mismatched Negativity – MMN) and behavioral measures (AX discrimination and forced-choice identification) were employed to examine perception of a nine-step vowel continuum, re-synthesized from natural tokens. Results revealed that (i) both monolingual and early bilinguals showed similar behavioral perception while late bilinguals performed more poorly on all behavioral tasks; and (ii) monolinguals showed robust evidence of discrimination (MMN) at a pre-attentive level that was significantly larger than found for either early or late bilinguals. These findings suggested that early input of English vowels to bilinguals did not necessarily lead to robust, automatic processing, as measured at a more attention-independent neural level; but earlier experience with a second language allowed for native-like speech perception measured with behavioral tasks.