Dioxane (diethylene oxide) is a synthetic organic compound classified as heterocyclic ether, a potentially carcinogenic water toxicant. Prolonged exposure can cause eye irritation, carcinogenic liver reactions, and other severe issues. Therefore, efficient dioxane detectors are needed to be designed and developed. Inspired by the recent developments of 2D materials in biosensing, in this work, the dioxane detection potentiality of pristine and metal-doped (Al, Au, and Ag) 2D VSe2 have been systematically examined using Density Functional Theory (DFT) based simulations. Among all the metallic dopants considered, Al binds energetically on the VSe2 surface with an energy of -2.158 eV. The adsorption of dioxane was studied by considering the electronic properties, adsorption energy, orbital interactions, and charge transfer. Our DFT calculation suggests that dioxane adsorption in Al-doped VSe2 is more promising than the pristine and other metal-doped VSe2 systems, due to the reasonable adsorption energy of -0.80 eV, charge transfer of -0.567e, and strong orbital interaction between Al 3p and O 2p orbitals. Additionally, the room temperature structural solidity of the sensor has also been verified using the ab initio molecular dynamics simulations. The reported theoretical results inspire the fabrication and engineering of efficient dioxane sensors using Al-doped VSe2.