Soft X-ray absorption spectra (XAS) and magnetic circular dichroism (XMCD) of Fe and Cu L2,3 edges have been measured on the triangular lattice antiferromagnet CuFeO2. By applying sum rule analysis to the XMCD of Fe, the ratio of the orbital to spin magnetic moments is determined to be −0.071. Because the nominal valence of Fe in CuFeO2 was Fe3+ (3d5), the orbital magnetic moment was considered to be zero in the past. However, the present research demonstrates that the orbital magnetic moment of Fe takes a finite value and it is possibly due to Fe4+ (3d4), which is considered to be responsible for the strong magnetic anisotropy and the ferroelectricity. We compare the experimental results with the results of ab initio multiplet calculations based on the configuration interaction theory and discuss the anomalous electronic structures of Fe and Cu ions in CuFeO2.