Highly active and durable catalysts are crucial for the development of direct alcohol fuel cells (DAFCs). Herein, a phosphorus and nickel oxide co-existed composite catalyst (Pd-NiOx-P/C) is prepared for glycerol electrooxidation in alkaline media. X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and energy dispersive X-ray (EDX) analysis reveal that the phosphorus and nickel oxide are co-existed in the Pd-NiOx-P/C composite catalyst. Compared with Pd/C catalyst, electrochemical measurements present that it has good electrocatalytic performance with higher electrochemically active surface area (EASA = 576.3 cm(2) mgpd(-1)), larger peak current (I-p = 0.3640 A mgpd(-1)) and lower activation energy (E-a = 21 kJ mol(-1)). More importantly, the Pd-NiOx-P/C exhibits high stability. It will be a promising Pd-based catalyst in DAFCs. (C) 2016 Elsevier B.V. All rights reserved.