Multicenter covalent pi-bonding between pi-conjugated radicals has been recently recognized as a novel and important bonding interaction. The Cope rearrangement of cyclo-biphenalenyl 9 is studied by exploring its potential energy surface with density functional theory ( DFT), and it is found that pi-bonding plays a critical role in the rearrangement process. Affected by this, the rearrangement of 9 takes place by a stepwise mechanism through an unusual pi-intermediate 10, of C 2 h symmetry, which can be characterized as a 2 x 13 pi + 2 x 2 pi system. The pi-intermediate has a long inter-phenalenyl distance of R approximate to 2.8 (A) over circle, which is shorter than the sum of the van der Waals radii displaying multicenter covalent pi-bonding between the two phenalenyl units. The energy of the pi-intermediate 10 is higher than that of the sigma-bonded reactant 9 by similar to 2 kcal/ mol according to the employed spin-restricted DFT. NMR chemical shift calculations support the sigma-bonded 9 as the global minimum. The calculated activation barrier of similar to 6 kcal/ mol for the Cope rearrangement is consistent with the stepwise mechanism. A covalent pi-bonding effect in the pi-intermediate 10 is demonstrated indirectly by the shortening of inter- naphthalene distance of the dianion and dication of the cyclophane 14 compared to that of its neutral counterpart. The unusual pi-bonded structure with a long inter-phenalenyl distance becomes the most stable structure for the ethano-bridged derivative 13, which should have observable paramagnetism according to the calculated paramagnetic susceptibility.