Classifier chain (CC) is a multi-label learning approach that constructs a sequence of binary classifiers according to a label order. Each classifier in the sequence is responsible for predicting the relevance of one label. When training the classifier for a label, proceeding labels will be taken as extended features. If the extended features are highly correlated to the label, the performance will be improved, otherwise, the performance will not be influenced or even degraded. How to discover label correlation and determine the label order is critical for CC approach. This paper employs Bayesian network (BN) to model the label correlations and proposes a new BN-based CC method (BNCC). First, conditional entropy is used to describe the dependency relations among labels. Then, a BN is built up by taking nodes as labels and weights of edges as their dependency relations. A new scoring function is proposed to evaluate a BN structure, and a heuristic algorithm is introduced to optimize the BN. At last, by applying topological sorting on the nodes of the optimized BN, the label order for constructing CC model is derived. Experimental comparisons demonstrate the feasibility and effectiveness of the proposed method.