The research reported in this article investigated how students learning Japanese or Russian as a third language (L3) perceived and produced word-initial stops in their respective target language and the link between perception and production. The participants in the study were 39 Chinese university students who spoke Mandarin Chinese as their first language (L1), English as their second language (L2), and Japanese or Russian as their L3. An L3 identification task, an L3 reading task, and an L2 reading task were used to investigate the learners' perception and production of word-initial stops. The results demonstrated that the phonetic similarity in different stop categories between L1, L2, and L3 contributed to learners' confusion in perception. On the contrary, L3 learners could perceive the new acoustic feature voicing lead, but found it difficult to produce L3 voiced stops. In addition, the study found a positive relationship between the perception and production of voiceless stops in the initial stage of L3 acquisition, but there was no correlation between the perception and production of voiced stops. Pedagogical implications for L3 speech learning are discussed on the basis of the results.