The electrochemistry, UV-vis spectrophotometry, photoluminescence, and electrogenerated chemiluminescence (ECL) of perylenedicarboxylic imide, perylenetetrasarboxylic diimide (PDI), terrylenetetracarboxylic diimide (TDI), and quaterrylenecarboxylic diimide (QDI) were investigated. All compounds undergo two reversible one-electron reductions and one reversible one-electron oxidation reaction. The first reduction potential shifts to less negative values and the potential for oxidation to less positive values for the diimide series with increasing size of the aromatic core. These changes in potential correlate well with orbital energies from molecular orbital calculations. The difference in potential between the first and second reduction waves decreased with increasing distance between the imide groups, so that TDI and QDI show only a single reduction wave, equivalent to a two-electron reduction. These reduction potentials provide estimates for the equilibrium constant for disproportionation of the radical anion. Very stable ECL spectra of PDI or TDI generated by sequential production of the radical cation and radical anion at an electrode were observed; these were identical to the photoluminescence spectra. A consideration of the energetics of the electron transfer reaction and the singlet energy leads to the conclusion that emission occurs mainly via generation of triplets followed by triplet-triplet annihilation (the T-route).