In this paper, a newly developed fiber-supported poly(quaternaryammomum bromide)s, which served as an efficient and recyclable supported phase-transfer catalyst in the spinning basket reactor for a series of nucleophilic substitutions, is reported. The fiber catalysts were designed and synthesized systematically from commercially available polyacrylonitrile fiber, and the properties of fiber samples at different stages were charactenzed in detail by sorts of technologies. Moreover, the nucleophilic substitutions mediated with fiber-supported phase-transfer catalyst exhibited high efficiency to afford a range of substituted products in excellent yields (91-98%) under mild conditions, and on this basis, a solid-liquid phase-transfer catalysis mechanism was proposed. Markedly, the spinning basket reactor with fiber catalyst in its impellers revealed prominent recyclability at least for 15 cycles, and the concise method of operation also exerted a good perspective application in chemical industry.