In this work, CuCo@C and CuCoS@C derived from an in-situ synthesis bi-metallic MOF HKUST-1/ZIF-67 (CuCo-MOF) were successfully fabricated by calcination and hydrothermal sulfide strategies. Morphology characterization results indicated that ZIF-67 grew uniformly on the surface of HKUST-1 to form CuCo-MOF. And, benefiting from bi-metallic MOFs precursors, the formed derivatives inherited and possessed good textural properties and dispersing well metal sites, which facilitated diffusions of molecules and enhancements of catalytic performances. In addition, carbon matrix produced in the materials further accelerated electron transporting properties, boosting HER and OER activities. Accordingly, in electrolytic water evaluations, CuCo@C and CuCoS@C showed good HER and OER performance, achieving 97 mV and 180 mV of overpotential at 10 mA cm−2 in an alkaline medium, respectively. Additionally, the catalysts exhibit long-term stabilities. Thus, this study provides a rational way for designing and constructing of high-efficient catalysts for H2 and O2 generations from electrolytic water processes. [ABSTRACT FROM AUTHOR]