1,4-Benzodioxane has long been a versatile template widely employed to design molecules endowed with diverse bioactivities. Its use spans the last decades of medicinal chemistry until today concerning many strategies of drug discovery, not excluding the most advanced ones. Here, more than fifty benzodioxane-related lead compounds, selected from recent literature, are presented showing the different approaches with which they have been developed. Agonists and antagonists at neuronal nicotinic, α₁ adrenergic and serotoninergic receptor subtypes and antitumor and antibacterial agents form the most representative classes, but a variety of other biological targets are addressed by benzodioxane-containing compounds.