Redox flow batteries, as a key long-duration energy storage technology underpinning new power systems, have become a strategic focus in global energy transition. Their industrialization process is highly dependent on performance breakthroughs and cost optimization of key materials. This study reviews global technological advancements and industrial development status of key materials for redox flow batteries. It examines the impact of these materials on economic viability and market demand of redox flow batteries, identifying multiple constraints facing China in this field: difficulty in simultaneously achieving a long lifespan and low cost; supply chain vulnerabilities due to high dependence on imported high-end materials; challenges in market acceptance and business model development; and insufficient policy and standards frameworks to support material innovation. The study proposes a phased development pathway for key materials, advocating for the evolution of the material system from the current mainstream "all-vanadium‒all‒fluorinated" route toward a "novel‒nonfluorinated" direction. It further recommends accelerating the large-scale application of flow batteries within zero-carbon energy systems by strengthening industrial chain collaboration, innovating business models aligned with material characteristics, and improving material standards and evaluation systems. These efforts will help China secure a proactive position in global energy competition.