Efficient resume parsing is critical for global hiring, yet the absence of dedicated benchmarks for evaluating large language models (LLMs) on multilingual, structure-rich resumes hinders progress. To address this, we introduce ResumeBench, the first privacy-compliant benchmark comprising 2,500 synthetic resumes spanning 50 templates, 30 career fields, and 5 languages. These resumes are generated through a human-in-the-loop pipeline that prioritizes realism, diversity, and privacy compliance, which are validated against real-world resumes. This paper evaluates 24 state-of-the-art LLMs on ResumeBench, revealing substantial variations in handling resume complexities. Specifically, top-performing models like GPT-4o exhibit challenges in cross-lingual structural alignment while smaller models show inconsistent scaling effects. Code-specialized LLMs underperform relative to generalists, while JSON outputs enhance schema compliance but fail to address semantic ambiguities. Our findings underscore the necessity for domain-specific optimization and hybrid training strategies to enhance structural and contextual reasoning in LLMs.