A study of the charge distribution in the 1-hydropyrenyl anion (2−), and of its regioselectivity toward electrophilic attack was undertaken. In order to obtain reliable information on the reactive positions in 2−, a model with the same conjugated system was prepared, which has its 1-position fixed with a spirocyclopentane ring. Highly resolved 1H and 13C NMR spectra of this spirotcyclopentane-1,1′-[1H]pyrenyl] anion (1−) and of 2− were obtained. These spectra could be completely assigned by means of COSY, NOESY, and 2D 1H-13C COSY techniques. According to the 13C NMR measurements, 5-C of 1− and 2− bears the highest negative charge. The results of PM3 semiempirical calculations support this finding and, furthermore, a large HOMO coefficient was calculated at the quaternary 3a-C of 2−, suggesting that this position is susceptible toward attack by soft electrophiles. In full agreement with the 13C NMR and PM3 results, 5-C of 1− and 2− show the highest reactivity toward electrophilic attack, while the quaternary 3a-C of 1− and 2− is attacked by soft electrophiles. These new results contradict earlier findings because until now, carbon atom 9-C of the 1-hydropyrenyl anion (2−) was assumed to be the most reactive position, and soft electrophiles were thought to attack 10a-C of 2−.