Relation extraction (RE) consistently involves a certain degree of labeled or unlabeled data even if under zero-shot setting. Recent studies have shown that large language models (LLMs) transfer well to new tasks out-of-the-box simply given a natural language prompt, which provides the possibility of extracting relations from text without any data and parameter tuning. This work focuses on the study of exploring LLMs, such as ChatGPT, as zero-shot relation extractors. On the one hand, we analyze the drawbacks of existing RE prompts and attempt to incorporate recent prompt techniques such as chain-of-thought (CoT) to improve zero-shot RE. We propose the summarize-and-ask (SumAsk) prompting, a simple prompt recursively using LLMs to transform RE inputs to the effective question answering (QA) format. On the other hand, we conduct comprehensive experiments on various benchmarks and settings to investigate the capabilities of LLMs on zero-shot RE. Specifically, we have the following findings: (i) SumAsk consistently and significantly improves LLMs performance on different model sizes, benchmarks and settings; (ii) Zero-shot prompting with ChatGPT achieves competitive or superior results compared with zero-shot and fully supervised methods; (iii) LLMs deliver promising performance in extracting overlapping relations; (iv) The performance varies greatly regarding different relations. Different from small language models, LLMs are effective in handling challenge none-of-the-above (NoTA) relation.