The regioselectivity in the hetero Diels–Alder reaction between nitrosoethylene 1 and 1-vinylpyrrolidine 2 has been studied by a comparative ELF bonding analysis along the IRC of the endo/ortho and endo/meta regioisomeric channels at the B3LYP/6-31G∗ level. Along the most favorable endo/ortho regioisomeric channel, the C–C σ bond is first formed by coupling of two pseudoradical centers located at the most electrophilic carbon of 1 and the most nucleophilic center of 2. Formation of these relevant pseudoradical centers, which depend on the total charge transfer process along the polar reaction, and not on the approach mode of each reagent, is well characterized by analysis of the atomic spin density in the radical anion of nitrosoethylene 1 and in the radical cation of vinylpyrrolidine 2.