Abstract The synthesis and the crystallographic characterization of two dialkylchromium complexes possessing a Tp* ligand, i.e. Tp*CrMe 2(DMAP) ( 4) and Tp*Cr(CH 2Ph) 2(DMAP) ( 5) (Tp*=hydrotris(3,5-dimethylpyrazolyl)borate; DMAP=4-dimethylaminopyridine), are described. Treatment of Tp*CrCl 2(DMAP) ( 3) with two equivalents of MeLi gave 4, while the complex 5 was prepared by the reaction of 3 with two equivalents of PhCH 2MgCl. These complexes were found to be thermally robust and quite stable to air and moisture. Distorted octahedral geometry around each chromium center of 4 and 5 has been determined by X-ray analysis, the chromium center being surrounded with three nitrogen atoms of the Tp* ligand at facial positions, one nitrogen atom of the DMAP ligand, and two carbon atoms. The two benzyl ligands of 5 were found to coordinate to the chromium center in η 1-fashion.