1,4-Dioxane (dioxane), an emerging groundwater contaminant, is frequently detected in landfill leachates with its structural analog, tetrahydrofuran (THF). Along with undesirable leakage of landfill leachates, dioxane and THF inevitably percolate into groundwater leading to a broader region of contamination. Cometabolic bioremediation is an effective approach to manage commingled THF and dioxane pollution. In this study, a newly isolated bacterium Arthrobacter sp. WN18 is able to co-oxidize dioxane with THF as the primary substrate. Meanwhile, the THF-induced thmADBC gene cluster was responsible for the dioxane degradation rate indicating THF monooxygenase is the essential enzyme that initializing α-hydroxylation of THF and dioxane. Further, γ-butyrolactone and HEAA were characterized as the key metabolites of THF and dioxane, respectively. In addition, WN18 can tolerate the inhibition of trichloroethylene (5.0 mg/L) as a representative of co-existing leachate constituent, and sustain its activity at various pH (5−11), temperatures (15–42 °C), and salinities (up to 4%, as NaCl wt). Like other Arthrobacter species, WN18 also exhibited the capability of fixing nitrogen. All this evidence indicates the feasibility and advantage of WN18 as a thmADBC-catalyzed inoculator to bioremediate co-contamination of THF and dioxane. Display omitted •The Arthrobacter sp. WN18 was first proved can co-degrade dioxane.•THF-induced thm gene organization that initially cleaved dioxane was identified.•The possible degradation pathway of dioxane and THF were proposed.•WN18 has been shown to degrade dioxane and THF under multiple adverse conditions.