Syntactic trees have been widely applied in relation extraction (RE). However, since parsing qualities are not stable on different text domains and a pre-defined grammar may not well fit the target relation schema, the introduction of syntactic structures sometimes fails to improve RE performances consistently. In this work, we study RE models with various unsupervised structures mined from pre-trained language models (e.g., BERT). We show that, similar to syntactic trees, unsupervised structures are quite informative for RE task: they are able to obtain competitive (even the best) performance scores on benchmark RE datasets (ACE05, WebNLG, SciERC). We also conduct detailed analyses on their abilities of adapting new RE domains and influence of noise links in those structures. The results suggest that unsupervised structures are reasonable alternatives of commonly used syntactic structures in relation extraction models.