Safety lies at the core of the development of Large Language Models (LLMs). There is ample work on aligning LLMs with human ethics and preferences, including data filtering in pretraining, supervised fine-tuning, reinforcement learning from human feedback, red teaming, etc. In this study, we discover that chat in cipher can bypass the safety alignment techniques of LLMs, which are mainly conducted in natural languages. We propose a novel framework CipherChat to systematically examine the generalizability of safety alignment to non-natural languages -- ciphers. CipherChat enables humans to chat with LLMs through cipher prompts topped with system role descriptions and few-shot enciphered demonstrations. We use CipherChat to assess state-of-the-art LLMs, including ChatGPT and GPT-4 for different representative human ciphers across 11 safety domains in both English and Chinese. Experimental results show that certain ciphers succeed almost 100% of the time in bypassing the safety alignment of GPT-4 in several safety domains, demonstrating the necessity of developing safety alignment for non-natural languages. Notably, we identify that LLMs seem to have a ''secret cipher'', and propose a novel SelfCipher that uses only role play and several unsafe demonstrations in natural language to evoke this capability. SelfCipher surprisingly outperforms existing human ciphers in almost all cases.