The higher-order cycloaddition (HOCA) reaction of tropone with cyclopentadiene (Cp) has been studied within the Molecular Electron Density Theory. The Electron Localization Function (ELF) analysis of the electronic structure of tropone and Cp characterizes the structural behaviors of the two conjugated unsaturated systems, while the conceptual DFT reactivity indices classify tropone as a strong electrophile and Cp as a strong nucleophile participating in polar cycloaddition reactions of reverse electron density flux. Eight competitive reaction paths have been characterized for this cycloaddition reaction. The most favorable one allowing the formation of the formal out [6 + 4] cycloadduct has an activation enthalpy of 16.2 kcal·mol−1, and the reaction is exothermic by −21.4 kcal·mol−1. This HOCA reaction, which takes place through a non-concerted two-stage one-step mechanism, presents high stereo-, pseudocyclic- and regioselectivities, explaining the exclusive formation of the experimental [6 + 4] cycloadduct. While the most favorable nucleophilic attack of Cp on most electrophilic C2 positions of tropone accounts for regioselectivities, the favorable electrostatic interactions present between the Cp framework and the negatively charged O8 oxygen of tropone account for the stereo- and pseudocyclic selectivities. Despite the symmetry of the two reagents, this HOCA reaction takes place via a highly asynchronous transition state structure as a consequence of the most favorable two-center interactions taking place between the electrophilic C2 center of tropone and the nucleophilic C9 center of Cp.