A mononuclear iron(III) complex, [FeCl2(phen)2][PF6]•MeCN [dichloridobis(1,10-phenanthroline-κ 2 N,N′)iron(III) hexafluoridophosphate-acetonitrile], was synthesized, and characterized by single-crystal X-ray method. The compound crystallized in the monoclinic space group C2/c and Z = 4 with cell parameters a = 16.3586(12)Å, b = 12.6022(9)Å, c = 13.0231(9)Å, β = 103.6760(10) , V = 2608.7(3)Å 3. The R1 [I > 2σ(I)] and wR2 (all data) values were 0.0345 and 0.0949, respectively, for all 3161 independent reflections. Analysis revealed that the complex cation has an octahedral coordination geometry with a Cl2N4 donor set with two chloride ligands at the cis-positions.