Metal-free Brønsted acids have emerged as a new and extremely efficient class of chiral organocatalysts. They have been extensively employed in a wide variety of chemical transformations, though their use in Diels-Alder reactions has not been thoroughly studied. On the basis of the privileged position of this cycloaddition transformation in modern organic chemistry, herein we wish to fully explore its asymmetric version using BINOL-derived Brønsted acids as chiral organocatalysts. This would allow the development of novel and efficient organocatalytic strategies for the synthesis of key enantiomerically pure frameworks, valuable in different applications, such as the synthesis of biologically active compounds.