The present electroencephalographical multi-speaker MMN oddball experiment was designed to study the phonological processing of German native and non-native speech sounds. Precisely, we focused on the perception of German /ɪ-iː/, /ɛ-ɛː/, /a-aː/ and the fricatives [ʃ] and [ç] in German natives (GG) and French learners of German (FG). As expected, our results showed that GG were able to discriminate all the critical vowel contrasts. In contrast, FG, despite their high L2 proficiency level, were only marginally sensitive to vowel length variations. Finally, neither GG nor FG discriminated the opposition between [ʃ] and [ç], as revealed by the absence of MMN response. This latter finding was interpreted in terms of low perceptual salience. Taken together, the present findings lend partial support to the Perceptual Assimilation Model for late bilinguals (PAM-L2) for speech perception of non-native phonological contrasts.