The structure of the isolated intermediate from the 4-tricyanovinylation of 2,6-dimethylaniline with tetracyanoethylene has been investigated. Ultraviolet, infrared, nuclear magnetic resonance, and mass spectra and dipole moment measurements as well as chemical evidence have been used. The evidence favours 2,6-dimethyl-4-(1,1,2,2-tetracyanoethyl)aniline (II) rather than the σ-complex (I). The tricyanovinylation mechanism is discussed.