Cross-Chart Retrieval-Augmented Generation (RAG) is critical for complex multi-modal analytical tasks in scientific, business, and political domains. However, existing benchmarks either focus on tables, which are well-structured and textualized, or generate cross-chart questions by simply extracting key points, which often induces lexical overlap between queries and evidence and yields logically inconsistent reasoning chains. To address this, we introduce ChartWalker, a novel framework for constructing challenging cross-chart RAG tasks. ChartWalker features a hierarchical knowledge graph construction method tailored to charts, which organizes entities and relations by granularity to preserve analytical structure. We then propose a structure-aware sampling algorithm that synthesizes semantically coherent, multi-hop reasoning paths, enabling explicit control over query difficulty and granularity for QA generation. Built with this framework, we release ChartWalker-Bench, a comprehensive benchmark spanning diverse domains and cross-chart query types. Extensive evaluations across major RAG paradigms reveal significant performance gaps, underscoring the benchmark's difficulty and utility. Furthermore, we provide ChartWalker-Agent, an agentic baseline to facilitate analysis and inspire future system design.