In this chapter, the synthesis of substituted 1,4-dioxanes and their saturated bridged, fused, and spirocyclic derivatives is discussed for the first time in Science of Synthesis. Partially unsaturated compounds, in particular benzo, 2-oxo, and related derivatives, are excluded from this review. Methods based on the construction of the 1,4-dioxane core, as well as on functionalization of the parent 1,4-dioxane and 2,3-dihydro-1,4-dioxine are presented.