Zero-Shot Composed Image Retrieval (ZS-CIR) aims to retrieve target images by integrating information from a composed query (reference image and modification text) without training samples. Existing methods primarily combine caption models and large language models (LLMs) to generate target captions based on composed queries but face various issues such as incompatibility, visual information loss, and insufficient reasoning. In this work, we propose CoTMR, a training-free framework crafted for ZS-CIR with novel Chain-of-thought (CoT) and Multi-scale Reasoning. Instead of relying on caption models for modality transformation, CoTMR employs the Large Vision-Language Model (LVLM) to achieve unified understanding and reasoning for composed queries. To enhance the reasoning reliability, we devise CIRCoT, which guides the LVLM through a step-by-step inference process using predefined subtasks. Considering that existing approaches focus solely on global-level reasoning, our CoTMR incorporates multi-scale reasoning to achieve more comprehensive inference via fine-grained predictions about the presence or absence of key elements at the object scale. Further, we design a Multi-Grained Scoring (MGS) mechanism, which integrates CLIP similarity scores of the above reasoning outputs with candidate images to realize precise retrieval. Extensive experiments demonstrate that our CoTMR not only drastically outperforms previous methods across four prominent benchmarks but also offers appealing interpretability.