The mechanism of electrophilic aromatic nitration was revisited. Based on the available experimental data and new high-level quantum chemical calculations, a modification of the previous reaction mechanism is proposed involving three separate intermediates on the potential energy diagram of the reaction. The first, originally considered an unoriented pi-complex or electron donor acceptor complex (EDA), involves high electrostatic and charge-transfer interactions between the nitronium ion and the a-aromatics. It explains the observed low substrate selectivity in nitration with nitronium salts while maintaining high positional selectivity, as well as observed oxygen transfer reactions in the gas phase. The subsequent second intermediate originally considered an oriented "pi-complex" is now best represented by an intimate radical cation-molecule pair, C6H6+/.NO2, that is, a SET complex, indicative of single-electron transfer from the aromatic a-system to NO2+. Subsequently, it collapses to afford the final a-complex intermediate, that is, an arenium ion. The proposed three discrete intermediates in electrophilic aromatic nitration unify previous mechanistic proposals and also contribute to a better understanding of this fundamentally important reaction. The previously obtained ICR data of oxygen transfer from NO2+ to the aromatic ring are also accommodated by the proposed mechanism. The most stable intermediate of this reaction on its potential energy surface is a complex between phenol and NO+. The phenol-NO+ complex decomposes affording C6H6O+./PhOH+ and NO, in agreement with the ICR results.