Excited state dynamics of trinary star-shaped dendritic compounds with triphenylamine arms and different cores were studied by means of time-resolved fluorescence and transient absorption. Under optical excitation, nonpolar C3 symmetry molecules form polar excited states localized on one of the molecular substituents. Conformational excited state stabilization of molecules with an electron-accepting core causes a formation of twisted internal charge transfer (TICT) states in polar solvents. A low transition dipole moment from TICT state to the ground state causes very weak fluorescence of those compounds and strong dependence on the solvent polarity. The compound formed from the triphenylamine central core and identical arms also experiences excited state twisting, however, weakly sensitive to the solvent polarity.