Deobfuscating binary code remains a fundamental challenge in reverse engineering, as obfuscation is widely used to hinder analysis and conceal program logic. Although large language models (LLMs) have shown promise in recovering semantics from obfuscated binaries, a systematic evaluation of their effectiveness is still lacking. In this work, we present BinDeObfBench, the first comprehensive benchmark for assessing LLM-based binary deobfuscation across diverse transformations spanning pre-compilation, compile-time, and post-compilation stages. Our evaluation shows that deobfuscation performance depends more on reasoning capability and domain expertise than on model scale, and that task-specific supervised fine-tuning consistently outperforms broad domain pre-training. Reasoning models can maintain robustness under severe obfuscation, generalize across different instruction set architectures (ISAs) and optimization levels. In-context learning benefits standard models but yields limited gains for reasoning models. Overall, our study highlights the importance of task-specific fine-tuning and reasoning-driven strategies, and positions BinDeObfBench as a basis for future work in binary deobfuscation.