This study reports syllable position effects on second language (L2) Portuguese speech perception, revealing that L2 segmental learning may be prone to an influence from the suprasegmental level. The results show that first language (L1) Mandarin learners had diminished performance on the discrimination between the target Portuguese liquids (/l/ and /[voiced alveolar tap or flap]/) and their position-dependent deviant productions, suggesting that the cause of their perceptual confusability differs across syllable positions. Another syllabic position effect was attested in the acquisition order (/l/[subscript onset] > /l/[subscript coda], /[voiced alveolar tap or flap]/[subscript coda] > /[voiced alveolar tap or flap]/[subscript onset]), demonstrating that an L2 sound is not mastered equally in all positions. Furthermore, we also observed that an increase in L2 experience affected only the perceptual identification accuracy of [l], but not of [[voiced alveolar tap or flap]]. This seems to suggest that L2 experience may exert different degrees of impact, depending on the L2 segments. Both theoretical and methodological implications of these results are discussed.