Abstract Multi-label classification is a challenging and appealing supervised learning problem where a subset of labels, rather than a single label seen in traditional classification problems, is assigned to a single test instance. Classifier chains based methods are a promising strategy to tackle multi-label classification problems as they model label correlations at acceptable complexity. However, these methods are difficult to approximate the underlying dependency in the label space, and suffer from the problems of poorly ordered chain and error propagation. In this paper, we propose a novel polytree-augmented classifier chains method to remedy these problems. A polytree is used to model reasonable conditional dependence between labels over attributes, under which the directional relationship between labels within causal basins could be appropriately determined. In addition, based on the max-sum algorithm, exact inference would be performed on polytrees at reasonable cost, preventing from error propagation. The experiments performed on both artificial and benchmark multi-label data sets demonstrated that the proposed method is competitive with the stateof-the-art multi-label classification methods.