Defect engineering through heteroatom doping is one of the most important strategies towards the development of catalytic active materials for energy related applications. Herein, a novel trifunctional Br/Co/N Co-doped and defect-enriched porous carbon framework (BrHT@CoNC) is designed, which shows excellent electrocatalytic activity for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) as well as the hydrogen evolution reaction (HER). Introduction of extensive defects by heteroatom-doping is simply achieved by pyrolysis of the surfactant, dimethyldioctadecylammonium bromide (DODAB) modified ZIF-67. The BrHT@CoNC composite shows great potential as an economical catalyst/electrode for both rechargeable Zn-air batteries and overall water splitting devices. This work opens a new avenue toward the exploration of cost effective heteroatom doped catalysts for efficient integration of three or more functions into one freestanding electrode.