The reaction of VCl3 with (S)-(-)-Na-2 (binol) (binol = 1,1'-bi-2-naphtholate) gave a new vanadium(III) complex, [Na(OEt2)](3)[V(binol)(3)] (Fig. 1). The X-ray crystallographic structure of this complex (Complex 1) in Figure 1 reveals its propeller-like structure, which is similar to those of the reported rare earth analogues. The complex showed moderate catalytic activities for ethylene polymerization upon activation with modified methylaluminoxane (MMAO) and with diethyl-aluminum chloride (DEAC). The Complex 1/DEAC system also catalyzed the polymerization of propylene to give atactic polypropylene with low activity. (C) 2003 Wiley Periodicals, Inc.