To address the green development requirements of power grids under new-generation power systems and mitigate global warming, the development of high-voltage vacuum circuit breakers (VCBs) is urgently required for environmentally substituting SF6. Among critical VCB components, the performance of electrical contact materials is fundamentally determinative of interrupting capacity, electrical endurance, and operational reliability. With large-scale renewable energy integration and ultra-high-voltage (UHV) grid expansion, contact materials are confronted with multifaceted technical challenges including elevated voltage classes (≥126 kV), high-current interruption (≥40 kA), and frequent switching operations. This review systematically examines the technological evolution of high-voltage VCBs and recent advances in contact materials, thereby establishing a research foundation for next-generation VCBs with enhanced voltage ratings and interrupting capabilities.