Non-precious materials have been considered as promising bifunctional catalysts towards oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). In the present work, a three dimensional (3D) Co-N co-doped hollow carbon sphere (HCS) electrocatalyst is synthesized at room temperature by the aid of a facile preparation method. The as obtained Co-N co-doped catalyst exhibits excellent catalytic activity towards both ORR and OER due to its high surface area and to 3D hollow architecture. For the ORR, the catalyst shows more positive onset-potential (of similar to 0.962 V vs. RHE) and larger diffusion limiting current density (5.55 mA cm(-2)) compared with benchmark Pt/C catalyst in alkaline medium. Moreover, the as synthesized catalyst exhibits low potential (1.720 V vs. RHE) at the current density of 10 mA cm(-2) and small Tafel slope (81 mV dec(-1)) for OER. In addition, the catalyst exhibits remarkable methanol tolerance and good long-term stability under working conditions. This strategy provides a facile and effective method for the preparation of non-noble metal catalysts with 3D hollow structure for energy conversion and storage applications. (C) 2017 Elsevier B.V. All rights reserved.