From the perspective of structural linguistics, we explore paradigmatic and syntagmatic lexical relations for Chinese POS tagging, an important and challenging task for Chinese language processing. Paradigmatic lexical relations are explicitly captured by word clustering on large-scale unlabeled data and are used to design new features to enhance a discriminative tagger. Syntagmatic lexical relations are implicitly captured by syntactic parsing in the constituency formalism, and are utilized via system combination. Experiments on the Penn Chinese Treebank demonstrate the importance of both paradigmatic and syntagmatic relations. Our linguistically motivated, hybrid approaches yield a relative error reduction of 18% in total over state-of-the-art baselines. Despite the effectiveness to boost accuracy, computationally expensive parsers make hybrid systems inappropriate for many realistic NLP applications. In this article, we are also concerned with improving tagging efficiency at test time. In particular, we explore unlabeled data to transfer the predictive power of hybrid models to simple sequence models. Specifically, hybrid systems are utilized to create large-scale pseudo training data for cheap models. Experimental results illustrate that the re-compiled models not only achieve high accuracy with respect to per token classification, but also serve as a front-end to a parser well.