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This paper investigates the nature of native Mandarin Chinese speakers’ phonotactic knowledge via an experimental study and formal modelling of the experimental results. Results from a phonological well-formedness judgement experiment suggest that Mandarin speakers’ phonotactic knowledge is sensitive not only to lexical statistics, but also to grammatical principles such as systematic and accidental phonotactic constraints, allophonic restrictions and segment–tone co-occurrence restrictions. We employ the UCLA Phonotactic Learner to model Mandarin speakers’ phonotactic knowledge, and compare the model's well-formedness predictions with speakers’ judgements. The disparity between the model's predictions and the well-formedness ratings from the experiment indicates that grammatical principles and the lexicon are still not sufficient to explain all of the variations in the speakers’ judgements. We argue that multiple biases, such as naturalness bias, allophony bias and suprasegmental bias, are effective during phonotactic learning.