To investigate how the electronic effect of ligand at donor site influences electronic communication or metal-to-metal charge transfer (MMCT) properties in similar mixed-valence (MV) complexes, a series of binuclear organometallic complexes, MeCp(dppe)RuCNFeCl₃ (1), MeCp(PPh₃)₂RuCNFeCl₃ (2), Cp*(dppe)FeCNFeCl₃ (3), Cp*(dppe)RuCNFeCl₃ (4) and Cp*(PPh₃)₂RuCNFeCl₃ (5), have been synthesized and characterized. The electronic absorptions of these complexes show the presence of MMCT properties between Ru^II or Fe^II and Fe^III ions, strongly supported by the theoretical calculations. With increasing electron-donating ability of ligands (PPh₃ > dppe, Cp* > MeCp) at donor site, the MMCT absorption bands are red-shifted, which expresses in the sequence of absorption bands with 1 (500 nm), 4 (536 nm), 2 (542 nm), 5 (580 nm) from high-energy to low-energy. Meanwhile, the MMCT absorption energy of 4 (536 nm) is larger than that of 3 (760 nm) due to the stronger electron-donating ability of Fe^II than Ru^II. Furthermore, these complexes belong to the Class II systems according to the Robin and Day’s classification.