We study generalizable policy learning from demonstrations for complex low-level control (e.g., contact-rich object manipulations). We propose a novel hierarchical imitation learning method that utilizes sub-optimal demos. Firstly, we propose an observation space-agnostic approach that efficiently discovers the multi-step subskill decomposition of the demos in an unsupervised manner. By grouping temporarily close and functionally similar actions into subskill-level demo segments, the observations at the segment boundaries constitute a chain of planning steps for the task, which we refer to as the chain-of-thought (CoT). Next, we propose a Transformer-based design that effectively learns to predict the CoT as the subskill-level guidance. We couple action and subskill predictions via learnable prompt tokens and a hybrid masking strategy, which enable dynamically updated guidance at test time and improve feature representation of the trajectory for generalizable policy learning. Our method, Chain-of-Thought Predictive Control (CoTPC), consistently surpasses existing strong baselines on various challenging low-level manipulation tasks with sub-optimal demos. See project page at https://sites.google.com/view/cotpc.