The development of multidimensional structured electrode materials with simple synthetic methods and their electrochemical sensing ability against environmental pollution is still a challenge. In this article, we propose a hybrid formed using multidimensional (3D/2D) vanadium diselenide microspheres and tungsten diselenide nanosheets (VSe 2 /WSe 2 ) for the electrochemical detection of 5-nitroquinoline (5-NQ), a highly toxic and hazardous substance that is polluting aquatic life due to increasing industrial activities. The 3D/2D VSe 2 /WSe 2 hybrids were prepared by a simple solvothermal method and their morphological and structural analysis was confirmed by various spectroscopy and analytical techniques such as powder X-ray diffraction, X-ray photoelectron spectroscopy, field emission scanning electron microscopy−energy dispersive X-ray spectroscopy, transmission electron microscopy, cyclic voltammetry, and differential pulse voltammetry. The proposed 3D/2D architecture showed a strong synergistic effect between the two components as well as high electrical conductivity. As a result, an increased peak current for the reduction and detection of 5-NQ was achieved compared to other modified and unmodified disposable screen-printed electrodes (SPE), such as bare SPE, VSe 2 /SPE, and WSe 2 /SPE. Under the optimized electrochemical conditions, VSe 2 /WSe 2 /SPE showed large linear response ranges (0.012−1053, 1183−3474 μM), a low detection limit (0.002 μM), good sensitivity along with good selectivity, and repeatability for the detection of 5-NQ. With this prominent electrochemical behavior, the VSe 2 /WSe 2 electrode has clear potential to produce high-performance sensor devices.