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The triplet state in π-conjugated polymers is difficult to detect owing to the absence of phosphorescence. However applications of electroluminescence from π-conjugated polymers have made a detailed understanding of these photophysical and photochemical processes essential. The role of the triplet state in polythiophenes is explored. Experimental evidence for the existence of the triplet state is presented, and its importance for estimates of the electron-electron Coulombic interaction discussed.