The development of urea oxidation reaction (UOR) and oxygen evolution reaction (OER) bifunctional electrocatalysts has dual significance in promoting hydrogen energy production and urea-rich wastewater treatment. Herein, a carboxylated multi-walled carbon nanotube (MWCNT-COOH)-ferrocene carboxylic acid (Fc-COOH) modulated NiMOF hybrid material (MWCNT-NiMOF(Fc)) has been synthesized for dual electrocatalysis of the UOR and OER. The material characterization results indicated that MWCNT-COOH and Fc-COOH were integrated into the framework structure of the NiMOF. The direct interaction between the NiMOF and MWCNT/Fc facilitated electron transfer in the hybrid material and led to lattice strain, which improved the charge transfer kinetics, promoted the exposure of more unsaturated Ni sites, and increased the electrochemically active surface area. These factors together enhanced the electrocatalytic activity of MWCNT-NiMOF(Fc) towards the UOR and OER. Using a glassy carbon electrode as the substrate, MWCNT-NiMOF(Fc) exhibited low potential requirements, low Tafel slopes, and high stability. In overall urea and water splitting electrolysis cells, the excellent UOR and OER dual functional catalytic ability and enormous practical application potential of the MWCNT-NiMOF(Fc) modified foam nickel electrode were further demonstrated. On the basis of the above research, the influence of a KOH environment on urea electrolysis was further studied, and the urea electrolysis products were analyzed, promoting a more comprehensive understanding of the catalytic performance of MWCNT-NiMOF(Fc) for urea oxidation. This study provides a new approach for developing high-performance NiMOF-based electrocatalysts for challenging bifunctional UOR/OER applications, and has potential application value in hydrogen production from urea-containing wastewater electrolysis.