Document Structured Extraction (DSE) aims to extract structured content from raw documents. Despite the emergence of numerous DSE systems, their unified evaluation remains inadequate, significantly hindering the field's advancement. This problem is largely attributed to existing benchmark paradigms, which exhibit fragmented and localized characteristics. To address these limitations and offer a thorough evaluation of DSE systems, we introduce a novel benchmark named READoc, which defines DSE as a realistic task of converting unstructured PDFs into semantically rich Markdown. The READoc dataset is derived from 3,576 diverse and real-world documents from arXiv, GitHub, and Zenodo. In addition, we develop a DSE Evaluation S$^3$uite comprising Standardization, Segmentation and Scoring modules, to conduct a unified evaluation of state-of-the-art DSE approaches. By evaluating a range of pipeline tools, expert visual models, and general VLMs, we identify the gap between current work and the unified, realistic DSE objective for the first time. We aspire that READoc will catalyze future research in DSE, fostering more comprehensive and practical solutions.