Compiler optimization is essential for improving program performance, yet modern compilers still depend on manually crafted transformation rules over intermediate representations (IRs). As compilers grow in complexity, maintaining these rule-based optimizations becomes increasingly labor-intensive and difficult to scale. Recent advances in large language models (LLMs) offer a promising alternative, but their effectiveness in compiler optimization remains limited—primarily due to the lack of IR-oriented datasets that expose models to diverse transformation samples in real-world scenarios (optimization-sensitive samples), hindering LLMs from learning rich and generalizable optimization strategies.In this paper, we introduce IR-OptSet, the first public optimization-sensitive dataset for advancing LLM-based IR optimizers. It comprises 170K LLVM IR samples from open-source repositories across 8 representative optimization domains. IR-OptSet defines two core tasks: Code Analysis and Optimized Code Generation, and provides tools for correctness verification, performance evaluation, and dataset expansion. In our experiments, fine-tuning three representative LLMs on IR-OptSet leads to significant accuracy improvements across both tasks. Moreover, the LLM fine-tuned with IR-OptSet outperforms traditional compiler with the -O3 option in 64 test cases in terms of performance. Further analysis reveals that IR-OptSet provides greater transformation diversity and representativeness than three widely used IR-oriented datasets, highlighting its potential to drive model-based IR optimization. IR-OptSet is publicly available at https://huggingface.co/datasets/YangziResearch/IR-OptSet.