Nonactivated arenes, such as benzene derivatives, are chemically inert due to their intrinsic aromaticity and low polarity. The catalytic asymmetric dearomatization (CADA, coined by You and co-workers) of the nonactivated arenes represents a formidable challenge. We herein demonstrated an organocatalytic asymmetric dearomatizing hetero-Diels-Alder reaction of benzene derivatives. The tunable regioselectivity of this strategy allowed delivery of a diversity of stereochemically complex polycyclic compounds and oxahelicenes with excellent stereoselectivity. The high complexity and three-dimensionality of the products are crucial for their potential applications in materials science and drug discovery. Mechanistic studies suggested that this reaction proceeds through a chiral tetra-substituted vinylidene ortho-quinone methide (VQM) intermediate, which is extremely active to overcome the loss of aromaticity of benzene derivatives with concomitant chirality transfer.