In this work, new strategies were developed to prepare 1D-V2MoO8 (VMO) rods from 2D V-doped MoSe2 nanosheets (VMoSe2) with good control over morphology and crystallinity by a facile hydrothermal and calcination process. The morphological changes from 2D to 1D rods were controlled by changing the calcination temperature from 300 to 600 °C. The elimination of Se and the incorporation of O into the V−Mo structure were evaluated by TGA, p-XRD, Raman, FE-SEM, EDAX, FE-TEM, and XPS analyses. These results prove that the optimization of the physical parameters leads to changes in the crystal phase and textural properties of the prepared material. The VMoSe2 and its calcined products were investigated as electrochemical sensors for the detection of the antibacterial drug nitrofurantoin (NFT). At a calcination temperature of 500 °C, the modified screen-printed carbon electrodes (SPCE) proved to be an excellent electrochemical sensor for the detection of NFT in neutral media. Under the optimized conditions, VMO-500 °C/ SPCE exhibits low detection limit (LOD) (0.015 μM), wide linear ranges (0.1−31, 47−1802 μM), good sensitivity, and selectivity. The proposed sensor was successfully used for the analysis of NFT in real samples with good recovery results. Moreover, the reduction potential of NFT agreed well with the theoretical analysis using quantum chemical calculations, with the B3LYP with 6- 31G(d,p) basis set predicting an E0 value of −0.45 V. The interaction between the electrode surface and NFT via the LUMO diagram and the electrostatic potential surface is also discussed