The widespread adoption of large language models (LLMs) across various regions underscores the urgent need to evaluate their alignment with human values. Current benchmarks, however, fall short of effectively uncovering safety vulnerabilities in LLMs. Despite numerous models achieving high scores and ‘topping the chart’ in these evaluations, there is still a significant gap in LLMs’ deeper alignment with human values and achieving genuine harmlessness. To this end, this paper proposes the first highly adversarial benchmark named FLAMES, consisting of 2,251 manually crafted prompts, ∼18.7K model responses with fine-grained annotations, and a specified scorer. Our framework encompasses both common harmlessness principles, such as fairness, safety, legality, and data protection, and a unique morality dimension that integrates specific Chinese values such as harmony. Based on the framework, we carefully design adversarial prompts that incorporate complex scenarios and jailbreaking methods, mostly with implicit malice. By prompting mainstream LLMs with such adversarially constructed prompts, we obtain model responses, which are then rigorously annotated for evaluation. Our findings indicate that all the evaluated LLMs demonstrate relatively poor performance on FLAMES, particularly in the safety and fairness dimensions. Claude emerges as the best-performing model overall, but with its harmless rate being only 63.08% while GPT-4 only scores 39.04%. The complexity of FLAMES has far exceeded existing benchmarks, setting a new challenge for contemporary LLMs and highlighting the need for further alignment of LLMs. To efficiently evaluate new models on the benchmark, we develop a specified scorer capable of scoring LLMs across multiple dimensions, achieving an accuracy of 77.4%. The FLAMES Benchmark is publicly available on https://github.com/AIFlames/Flames