The invention relates to a preparation method of high-performance organic fibers, particularly a preparation method of high-performance organic fibers on the basis of 4,4'-diaminodiphenyl ether. The invention aims to solve the common problems of poor interfacial binding property and low interfacial shear strength between fibers and resin substrate due to smooth surface, low activity and low soakage tendency with resin in the traditional PBO (poly(p-phenylene-2,6-benzobisoxazole)) fibers. The method comprises the following steps: adding 4,6-diamino-resorcinol hydrochloride, 4,4'-diaminodiphenyl ether, 2,5-dihydroxyterephthalic acid, polyphosphoric acid and phosphorus pentoxide into a polymerization kettle, dissolving by heating, adding phosphorus pentoxide, heating, adding polymethylphenylsiloxane, heating, filtering, degassing, extruding, preparing protofibrils, washing with water, washing with alcohol, washing with alkali, drying, and heating in a nitrogen protective atmosphere to obtain the high-performance organic fibers. The tensile strength of the high-performance organic fibers reaches 2.5-5.5 GPa. The invention is applicable to the field of preparation of organic fibers.