We assess the accuracy of the LHFX Time-Dependent Density-Functional Theory (TD-DFT) approach, which uses Kohn–Sham orbitals and eigenvalues from the Localized Hartree–Fock (LHF) method and the exchange-only adiabatic local density approximation kernel. We compute 172 singlet and triplet excitation energies of π → π∗, n → π∗, σ → π∗ and Rydberg character, for organic molecules of different size. We find that the LHFX method, which is free from the Self-Interaction-Error (SIE) and from empirical parameters, outperforms the state-of-the-art hybrid TD-DFT approaches, and provides the same accuracy for all different classes of excitations. The SIE-free Kohn–Sham orbitals can be thus considered as starting point for TD-DFT developments.