The performance of multistate density functional theory (MSDFT) with nonorthogonal state interaction (NOSI) is assessed for 100 vertical excitation energies against the theoretical best estimates extracted to the full configuration interaction accuracy on the database developed by Loos et al. in 2018 (Loos2018). Two optimization techniques, namely, block-localized excitation and target state optimization, are examined along with two ways of estimating the transition density functional (TDF) for the correlation energy of the Hamiltonian matrix density functional. The results from the two optimization methods are similar. It was found that MSDFT-NOSI using the spin-multiplet degeneracy constraint for the TDF of spin-coupling interaction, along with the M06-2X functional, yields a root-mean-square error (RMSE) of 0.22 eV, which performs noticeably better than time-dependent density functional theory (DFT) at an RMSE of 0.43 eV using the same functional and basis set on the Loos2018 database. In comparison with wave function theory, NOSI has smaller errors than CIS(D∞), LR-CC2, and ADC(3) all of which have an RMSE of 0.28 eV, but somewhat greater than STEOM-CCSD (RMSE of 0.14 eV) and LR-CCSD (RMSE of 0.11 eV) wave function methods. In comparison with Kohn-Sham (KS) DFT calculations, the multistate DFT approach has little double counting of correlation. Importantly, there is no noticeable difference in the performance of MSDFT-NOSI on the valence, Rydberg, singlet, triplet, and double-excitation states. Although the use of another hybrid functional PBE0 leads to a greater RMSE of 0.36 eV, the deviation is systematic with a linear regression slope of 0.994 against the results with M06-2X. The present benchmark reveals that density functional approximations developed for KS-DFT for the ground state with a noninteracting reference may be adopted in MSDFT calculations in which the state interaction is key.