Mott gap excitations in the optimally doped high-T(c) superconductor YBa(2)Cu(3)O(7-delta) (T(c)=93 K) have been studied by the resonant inelastic x-ray scattering method. Anisotropic spectra in the ab plane are observed in a twin-free crystal. The excitation from the one-dimensional CuO chain is enhanced at 2 eV near the zone boundary of the b* direction, while the excitation from the CuO2 plane is broad at 1.5-4 eV and almost independent of the momentum transfer. Theoretical calculations based on the one-dimensional and two-dimensional Hubbard model reproduces the observed spectra when different values of the on-site Coulomb energy are assumed. The Mott gap of the CuO chain site is found to be much smaller than that of the CuO2 plane site.