A new and metal-free approach to the synthesis of substituted 6H-benzo[c]chromenes has been developed. This three-step synthetic sequence starts from variously substituted salicylaldehydes and α,β-unsaturated carbonyl compounds to form the chromene core. The de novo ring-forming key step is based on a highly regioselective intermolecular Diels-Alder cycloaddition between 3-vinyl-2H-chromenes and methyl propiolate, followed by oxidative aromatization of the cyclohexadiene cycloadduct intermediate to obtain the final products in good yields (up to 94% over two steps). A modular and divergent design was followed, including a multicomponent reaction, to maximize the scaffold diversity obtained from our approach. The mechanism, investigated by DFT calculations, was confirmed to be concerted through a slightly asynchronous transition state. Energetic analysis of the transition states which have been found confirmed the experimental results in terms of regioselectivity and reactivity tendencies.