A quantitative addition reaction between aromatic amino-substituted alkynes and tetracyanoethylene (TCNE), yielding donor-substituted tetracyanobutadiene chromophores, was for the first time employed as a click-type reaction to improve the thermal and optoelectronic properties of aromatic polyamines. The first reduction potentials or the LUMO levels of the aromatic polyamines were found to linearly decrease by the stepwise TCNE addition.