The invention discloses a composite nanofiber material and preparation and application thereof. The composite nanofiber material particularly relates to purification treatment on organic micro-pollutants degradation-resistant in water. The composite nanofiber material is composed of a rear earth oxide substrate and metal nanoparticles dispersed inside the substrate or on the surface of the substrate, wherein the substrate is the oxides of at least one rear earth element selected from Ce, Pr, Nd, Sm, Gd, Dy, Ho, Er and Yb; the metal nanoparticles are transition metal elements such as nickel, iron, cobalt and copper. By combining the triple effects of the transition metal nanoparticles, the rear earth oxides and interfacial effects, the composite nanofiber material with ultrafast pollutant treatment effects can be obtained and can be widely applied to various degradation-resistant water pollutants derived from industry, agriculture and medical industry. Besides, the composite nanofiber material is simple in materials and preparation, free from secondary pollution and reusable, reduces the water treatment cost and has a broad application prospect.