Dioxane is used in a variety of applications as a versatile aprotic solvent, e. g. for inks, adhesives, and cellulose esters. It is substituted for tetrahydrofuran (THF) in some processes, because of its lower toxicity and higher boiling point (101 °C, versus 66 °C for THF).
While diethyl ether is rather insoluble in water, dioxane is miscible and in fact is hygroscopic.  At standard pressure, the mixture of water and dioxane in the ratio 17.9:82.1 by mass is a positive azeotrope that boils at 87.6 C.
The oxygen atoms are weakly Lewis-basic. It  forms adducts with a variety of Lewis acids. It is classified as a hard base and its base parameters in the ECW model are E =1.86 and C = 1.29. 
Dioxane produces coordination polymers by linking metal centers.   In this way, it is used to drive the Schlenk equilibrium, allowing the synthesis of dialkyl magnesium compounds. Dimethylmagnesium is prepared in this manner:
:2 CHMgBr + (CHO) → MgBr(CHO) + (CH)Mg