We have studied the local electronic structure of LaMn(0.5)Co(0.5)O(3) using soft-x-ray absorption spectroscopy at the Co-L(3,2) and Mn-L(3,2) edges. We found a high-spin Co(2+)-Mn(4+) valence state for samples with the optimal Curie temperature. We discovered that samples with lower Curie temperatures contain low-spin nonmagnetic Co(3+) ions. Using soft-x-ray magnetic circular dichroism, we established that the Co(2+) and Mn(4+) ions are ferromagnetically aligned. We also revealed that the Co(2+) ions have a large orbital moment: morb/mspin approximate to 0.47. Together with model calculations, this suggests the presence of a large magnetocrystalline anisotropy in the material and predicts a nontrivial temperature dependence for the magnetic susceptibility.