Polycationic high-spin states of star-burst molecules based on (diarylamino)benzenes have been studied by cw and pulsed ESR spectroscopy. An electron spin transient nutation (ESTN) method based on pulsed ESR spectroscopy was applied to the dicationic and tricationic high-spin states of N,N,N’,N’-tetra(4- anisyl)-2,4-dimethyl-1,5-phenylenediamine and N,N,N’,N’,N",N"-hexa(4-anisyl)-1,3,5-triaminobenzene, respectively, in order to identify the spin multiplicity of the polycationic states. The observed 2D nutation spectra of the dicationic and tricationic states unequivocally showed that the dicationic and tricationic states are ground-state triplet and quartet, respectively.