Transition metal and nitrogen co-doping into carbon is an effective approach to promote the catalytic activities towards oxygen reduction reaction (ORR) and/or oxygen evolution reaction (OER) in the resultant electrocatalysts, M/N-C. The preparation of such catalysts, however, is often complicated and in low yield. Herein we report a robust approach for easy synthesis of M/N-C hybrids in high yield, which includes a mussel-inspired polymerization reaction at room temperature and a subsequent carbonization process. With the introduction of selected transition metal salts into aqueous solution of dopamine (DA), the obtained mixture self-polymerizes to form metal-containing ploydopamine (M-PDA) composites, e.g. Co-PDA, Ni-PDA and Fe-PDA. Upon carbonization at elevated temperature, these metal-containing composites were converted into M/N-C, i.e. Co-PDA-C, Ni-PDA-C and Fe-PDA-C, respectively, whose morphologies, chemical compositions, and electrochemical performances were fully studied. Enhanced ORR activities were found in all the obtained hybrids, with Co-PDA-C standing out as the most promising catalyst with excellent stability and catalytic activities towards both ORR and OER. This was further proven in Zn-air batteries (ZnABs) in terms of discharge voltage stability and cycling performance. At a discharge-charge current density of 2 mA cm-2 and 1 hr per cycle, the Co-PDA-C based ZnABs were able to steadily cycle up to 500 cycles with only a small broadening in the discharge-charge voltage gap which notably outperformed Pt/C; At a discharge current density of 5 mA cm-2, the battery continuously discharged for more than 540 h with the discharge voltage above 1 V and a voltage drop rate of merely 0.37 mV h-1. With simplicity and scalability of the synthetic approach and remarkable battery performances, the Co-PDA-C hybrid catalyst is anticipated to play an important role in practical ZnABs.