A simple hydrothermal synthesis approach was used to synthesize porous MgNiO2 Chrysanthemum Flowers (CFs) nanostructures and applied as a sensing electrode for quick detection of hazardous mercury (Hg2+ ions). The morphological, structural, and electrochemical properties of MgNiO2 CFs were investigated. The morphological characteristic of MgNiO2 CFs, with a specific surface area of 45.618 m2/g, demonstrated strong electrochemical characteristics, including cations in different oxidation states of Ni3+/Ni2+. Using a three-electrode system for electrochemical detection, the MgNiO2 CFs based electrode revealed a good correlation coefficient (R2) of ~0.9721, a limit of detection (LOD) of ~11.7 μM, a quick response time (10 s), and a sensitivity of 8.22 μA∙μM−1∙cm−2 for Hg2+ ions over a broad linear range of 10–100 μM. Moreover, the selectivity for Hg2+ ions in tap water and drinking water was determined, and a promising stability of 25 days by MgNiO2 CFs electrode was exhibited. The obtained results indicate that the developed MgNiO2 CFs are a promising electrode for detecting hazardous Hg2+ ions in water and have the potential to be commercialized in the future.