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Tool learning is widely acknowledged as a foundational approach or deploying large language models (LLMs) in real-world scenarios. While current research primarily emphasizes leveraging tools to augment LLMs, it frequently neglects emerging safety considerations tied to their application. To fill this gap, we present ToolSword, a comprehensive framework dedicated to meticulously investigating safety issues linked to LLMs in tool learning. Specifically, ToolSword delineates six safety scenarios for LLMs in tool learning, encompassing malicious queries and jailbreak attacks in the input stage, noisy misdirection and risky cues in the execution stage, and harmful feedback and error conflicts in the output stage. Experiments conducted on 11 open-source and closed-source LLMs reveal enduring safety challenges in tool learning, such as handling harmful queries, employing risky tools, and delivering detrimental feedback, which even GPT-4 is susceptible to. Moreover, we conduct further studies with the aim of fostering research on tool learning safety. The data is released in https://github.com/Junjie-Ye/ToolSword.