Fluorine (F) has substantial social and environmental significance. Despite its high natural abundance, which often leads to the neglect of its sustainable management, its primary source, fluorspar, is limited and nonrenewable. As the world's largest producer and consumer of F resources, China encounters considerable challenges in managing these resources sustainably. However, a comprehensive understanding of F flows across China's economy has been notably absent. This study establishes a national-level material flow analysis (MFA) framework to examine the circulation and accumulation of F substances across various sectors in China from 2000 to 2020. The MFA encompasses over 200 F-containing products and 15 key sectors, tracking F flows through the stages of production, manufacturing, use, and waste management. Key findings show that China's F resource supply increased from 2297.9 kt in 2000 to 6392.2 kt in 2020, with 91.1% sourced from domestic ore mining. F consumption for manufacturing F-containing products rose from 270.1 to 2462.9 kt over the same period. Traditional sectors like metallurgy, cement production, and electrolytic aluminum dominated F consumption, while emerging sectors like photovoltaics experienced rapid growth. China has been a net exporter of F resources, with exports totaling 14,732.3 kt compared to 1931.1 kt of imports over the two decades. Nonetheless, China's role in global F trade has shifted from primarily exporting ores to becoming a major producer and exporter of F-containing products. This study provides a comprehensive analysis to date of China's F resource flows, offering critical insights for policymakers and industry stakeholders to enhance sustainable F management practices and address key challenges related to resource supply, utilization efficiency, and environmental impacts.