A survey of the spontaneous reactions of electrophilic olefins and nucleophilic olefins is presented as an area in which organic chemistry merges with polymer chemistry. The products include both small molecules and polymers, arising via tetramethylene biradical zwitterions that can cyclize or initiate polymerizations. Electrophilic tri- and tetrasubstituted olefins are particularly useful in delineating the transition from radical chemistry to ionic chemistry. A periodic table embodying these results enables predictions. Charge-transfer complexes, although observed in many of these reactions, play no significant role. Various aspects arising from these investigations include new cationic initiators, Lewis acid catalysis, quinodimethane chemistry, and photochemistry. (C) 2004 Wiley Periodicals, Inc.