The first crystal structure of a phenylcyanamide Rh(III) complex, [Rh(terpy)(bpy)(2,5-Cl₂pcyd)](PF₆)₂ (terpy = 2,2΄:6′,2″– terpyridine, bpy= 2,2΄-bipyridine, and 2,5-Cl₂pcyd = 2,5-dichlorophenylcyanamide) has been reported in this paper. Crystals of [Rh(terpy)(bpy)(2,5-Cl₂pcyd)](PF₆)₂ .0.5CH₃CN were grown by ether diffusion into an acetonitrile solution of the complex. Crystal structure data: orthorhombic system, space group Fdd2, with a = 84.228(3), b = 8.7162(3), c = 21.4921(7)Å, V=15778.4(9) ų, and Z=16. The structure was refined by using 4971 independent reflections with I>2σ(I) to a R factor of 0.0644 and R_w = 0.1752. ORTEP drawing of [Rh(terpy)(bpy)(2,5-Cl₂pcyd)](PF₆)₂ .0.5CH₃CN shows that the terpy and bpy ligands are coordinated to the Rh^III through their nitrogen atoms in a mutually perpendicular fashion. The anionic cyanamide group is coordinated end-on by the nitrile nitrogen to the Rh^III. The Rh^III –NCN bond is bent, having an angle of 125.4^o. This bent bond is largely determined by the σ-bonding interaction of a cyanamide non-bonding electron pair in a sp² hybrid orbital.