arXiv:2510.04040v1 Announce Type: new Abstract: Large language models (LLMs) increasingly rely on Chain-of-Thought (CoT) prompting to improve problem-solving and provide seemingly transparent explanations. However, growing evidence shows that CoT often fail to faithfully represent the underlying reasoning process, raising concerns about their reliability in high-risk applications. Although prior studies have focused on mechanism-level analyses showing that CoTs can be unfaithful, they leave open the practical challenge of deciding whether a specific trajectory is faithful to the internal reasoning of the model. To address this gap, we introduce FaithCoT-Bench, a unified benchmark for instance-level CoT unfaithfulness detection. Our framework establishes a rigorous task formulation that formulates unfaithfulness detection as a discriminative decision problem, and provides FINE-CoT (Faithfulness instance evaluation for Chain-of-Thought), an expert-annotated collection of over 1,000 trajectories generated by four representative LLMs across four domains, including more than 300 unfaithful instances with fine-grained causes and step-level evidence. We further conduct a systematic evaluation of eleven representative detection methods spanning counterfactual, logit-based, and LLM-as-judge paradigms, deriving empirical insights that clarify the strengths and weaknesses of existing approaches and reveal the increased challenges of detection in knowledge-intensive domains and with more advanced models. To the best of our knowledge, FaithCoT-Bench establishes the first comprehensive benchmark for instance-level CoT faithfulness, setting a solid basis for future research toward more interpretable and trustworthy reasoning in LLMs.