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Porous CuO-CdO nanofibers with mean diameter of 463 nm and high surface-to-volume ratio were prepared by impregnating electrospun carboxylic-functionalized poly(arylene ether ketone) (PCA-PAEK) nanofibrous webs with metal acetate solution and subsequent calcination. The special morphology was demonstrated to be decided by ion exchange reaction between metal ions and functional groups on polymer. TGA and EDX analysis confirmed that Cd2+ was more readily to react with PCA-PAEK than Cu2+, and the amount of Cu2+ can be decreased by overloading of Cd2+, leading to the degradation of sensing performance. FT-IR proved the existence of the ion exchange reaction and demonstrated the products were highly pure CuO-CdO compounds with EDX and XRD spectra. The products detailedly investigated for direct electrocatalytic oxidation of glucose evaluated cyclic voltammetry and chronoamperometry. CuO-CdO nanofibers modified electrodes exhibited superiorities of good anti-interference, low detection limit and fast response of glucose, attributing to the enhanced conductivity brought by CdO, good electrocatalytic activity brought by CuO and large surface area brought by porous structure. The simple strategy of electrospinning porous nanofibers using PCA-PAEK as templates and combined CuO and CdO with good electrooxidation glucose functions opens a new route to generate novel conductive metal oxide hybrid nanofibers applied for glucose enzymeless sensors. [ABSTRACT FROM AUTHOR]