Novel copoly (phthalazinone biphenyl ether ketone) (PPBEK) superfine fibrous membrane was successfully fabricated through electrospinning, and characterized by SEM, DSC, TGA and tensile test. The solution concentration of PPBEK suited for electrospinning was 0.10-0.30 g mL(-1), and the average diameter of PPBEK fibers increased obviously with the increase of solution concentration. The electrospun PPBEK superfine fibrous membrane had very high glass transition temperature (>242 degrees C), excellent tensile strength (4.94-18.66 MPa) and superior chemical resistance, which were critical advantages for the membrane as plating template applied in fuel cells. Pd was deposited on the PPBEK fibrous template by electroless plating with a layer thickness of similar to 250 nm. TEM shows that Pd nanoparticles dispersed well on PPBEK fibers and the diameter was about 4 nm. The as-prepared Pd/PPBEK superfine fibrous membrane had good conductivity and was successfully applied as free-standing electrocatalytic electrode for methanol oxidation without using any conductive support. (C) 2015 Elsevier B.V. All rights reserved.