Novel thiolation poly (phthalazinone ether ketone) (PPEK-SH) nanofibrous membrane (NFM) was successfully fabricated via grafting and electrospinning. The PPEK-SH NFM with high glass transition temperature (324.4 degrees C), robust tensile strength (12.48 MPa), high porosity (89.5%) and superior chemical resistance was employed as support of Au nanoparticles (NPs) for preparing electrocatalyst. Au NPs were deposited on the NFM via electroless plating and characterized by SEM, EDX, TEM and XRD. The as prepared Au/PPEK-SH NFM inherited the excellent properties of PPEK-SH NFM and good conductivity of Au, thereby was successfully used as a free-standing electrocatalyst without resorting to any conductive support. The free-standing NFM exhibited excellent electrocatalytic activity towards glycerol oxidation with high oxidation peak of 74.2 mA cm(-2) and low onset potential of -0.34 V. More importantly, benefiting from the strong chemical interaction between Au and -SH, Au/PPEK-SH NFM presented an incredible stability during the process of glycerol electrooxidation. Only 2.7% decrease of the peak current density was observed after 100 cycles of experiments, indicating that the free-standing electrocatalyst had great potential for long-term use. This work may provide a new approach for the development of stable free-standing electrocatalyst based on electrospun nanofibers in the application of direct alcohol fuel cells. (C) 2018 Elsevier B.V. All rights reserved.