2,6-Dicyanoaniline (DCA) reveals remarkably different physicochemical and spectral properties than other aniline derivatives. The infrared and Raman spectra for DCA in solid state and laser induced fluorescence (LIF) excitation spectra of vacuum jet cooled molecules have been investigated. The ground S 0 and the S 1 (B 2 ) excited state geometries, charge distributions and vibrational frequencies of DCA have been evaluated by ab initio calculations. The Dushinsky matrices have been applied for the mode correlation and assignments of the transition frequencies in LIF excitation spectra of DCA(NH 2 ) and DCA(ND 2 ). The intensity distributions in LIF excitation spectra were modeled. The dominant vibronic bands in the excitation spectra are connected with motions of the adjacent cyano- and amino groups. The transitions involving inversion motion of the amino group have low intensities.