The fluorescence lifetimes of the alpha,omega-diphenylpolyenyl carbocations in CH2Cl2 solution increase with decreasing temperature toward limiting values. This behavior is very similar to that of the corresponding alpha,omega-diphenylpolyenyl carbanions, and the quantitative differences are surprisingly small. By analogy with the anions, it is proposed that deactivation of the excited state occurs by fluorescence, internal conversion, and by skeletal twisting of these conformationally labile ions. This last method of deactivation is an activated process and becomes negligible at low temperatures.