Waterborne organic pollutants pose significant threats to ecosystems and the health of billions worldwide, presenting a pressing global challenge. Advanced oxidation processes (AOPs) offer promise for efficient wastewater treatment, yet the efficacy and the reliability of current environmental catalysts hinder their widespread adoption. This study developed an as-cast nanostructured glassy fiber capable of rapidly activating persulfate and achieved the degradation of diverse organic contaminants within 60 s using the as-prepared fiber. The material is relatively robust and can be reused about 40 times. The exceptional catalytic performance of the fibers stemmed from their low atomic coordination numbers, which facilitated the generation of numerous unsaturated active sites and accelerated radical production rates through a one-electron transfer mechanism. Additionally, the glassy-nanocrystalline heterogeneous interface, achieved through our proposed nanostructuralization approach, exhibited electron delocalization behavior. This enhanced persulfate adsorption and reduced the energy barrier for heterolytic cleavage of peroxy bonds. These findings present a novel avenue for the rational structural design of high-performance environmental catalysts for advanced water remediation.