We examined the neurophysiological underpinnings of lexical-tone and vowel-quality perception in learners of a non-tonal language. We tested 25 6- and 25 9-month-old German-learning infants, as well as 24 German adults and expected developmental differences for the two linguistic properties, as they are both carried by vowels, but have a different status in German. In adults, both lexical-tone and vowel-quality contrasts elicited mismatch negativities, with a stronger response to the vowel-quality contrast. Six-month-olds showed positive mismatch responses for lexical-tone and vowel-quality contrasts, with an emerging negative mismatch response for vowel-quality only. The negative mismatch responses became more pronounced for the vowel-quality contrast at 9 months, while the lexical-tone contrast elicited mainly positive mismatch responses. Our data reveal differential developmental changes in the processing of vowel properties that differ in their lexical relevance in the ambient language.