Ensuring the safety of Large Language Models (LLMs) is critical for real-world deployment. However, current safety measures often fail to address implicit, domain-specific risks. To investigate this gap, we introduce a dataset of 3,000 annotated queries spanning education, finance, and management. Evaluations across 14 leading LLMs reveal a concerning vulnerability: an average jailbreak success rate of 57.8\%. In response, we propose MENTOR, a metacognition-driven self-evolution framework. MENTOR performs metacognitive self-assessment, using strategies such as perspective-taking and consequential reasoning to uncover latent model misalignments. MENTOR couples single-pass rule-guided inference for routine requests with a selectively invoked metacognitive evolution cycle that revises residual unsafe responses, distills successful corrections into a dynamic rule graph, and compiles validated rules into activation-level steering signals for future inference. Experiments demonstrate that MENTOR substantially reduces attack success rates across all tested domains and outperforms existing safety alignment methods. The code and dataset for MENTOR are available at: https://anonymous.4open.science/r/MENTOR-Evo.

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