The first crystal structure of a phenylcyanamide cobaltoxime (cobaloxime) complex is reported. This compound is trans-[Co((DO)(DOH)pn)(2,5-Cl₂pcyd)₂], and consits of an imine-oxime equatorial ligand ((DO)(DOH)pn) and two 2,5-dichlorophenylcyanamide ligands in axial positions. Crystals of trans- [Co((DO)(DOH)pn)(2,5-Cl₂pcyd)₂] were grown by ether diffusion into an acetonitrile solution of the complex. Crystal structure of this complex is orthorhombic (space group: Pbca) with a = 13.6800, b = 13.7434, c = 29.892 Å, and Z = 8. The structure was refined by using 2946 independent reflections with I>2σ(I) to a R factor of 0.0606. Both phenylcyanamide ligands are coordinated to Co(III) through the terminal nitrile nitrogen of the cyanamide group. In addition, the cobalt(III)-cyanamide (Co(III)-N=C=N-ph) bond angle is significantly bent while the cyanamide group(N=C=N-) is largely coplanar with the phenyl ring. These geometries can be ascribed to the relative importance of p bonding.