Electrogenerated chemiluminescence (ECL) arising from the reaction of radical ions has previously be shown to arise from a variety of states including excited singlets, triplets, excimers, and exciplexes. In this work we describe two systems that form emissive states in ECL with different properties than those when formed with photoluminescence. The first system involves the reaction of the anthracene radical anion with the radical cation of 4,N,N-trimethylaniline. ECL from this system exhibited an exciplex whose energy and intensity relative to the emission from the anthracene singlet could be tuned by adjusting the solvent permittivity and ionic strength. Under conditions considered extreme for electrochemical experiments, no added electrolyte in dimethoxyethane, the relative intensity of the anthracene-related exciplex, formed from the encounter complex, was 8 times greater and red-shifted from that generated by photoluminescence in the same solution with 100-fold exciplex partner added. In the second system examined, the benzophenone radical anion reacted with the radical cation of either phenoxathiin or 4-methoxythioanisole; the ECL emission was from the benzophenone triplet state and an excimer. The excimer, a species not seen with photoluminescence, predominated as the benzophenone concentration was elevated into the low millimolar range. The results from these two simple systems clearly demonstrate that the radical ion annihilation pathway of ECL can generate different emissive states than those formed following photoexcitation.