AbstractSeveral CW–V catalysts were prepared by supporting VCl4 on Mg Cl2 with ethyl benzoate and CH–V catalysts prepared by reacting MgCl2.ROH, phthalic anhydride, and VCl4. These vanadium catalysts, activated with TEA (triethyl aluminum)/MPT (methyl‐p‐toluate) produce mainly (88–96%) refluxing n‐heptane insoluble isotactic PP. The active site has \documentclass{article}\pagestyle{empty}\begin{document}$ k_{p,i} = 1580 \left( M {\rm s} \right)^{ - 1}, k_{tr,i}^{\rm A} = 2 \times 10^{ - 3} {\rm s}^{ - 1} , k_{tr}^{\rm H} = 3.8 \times 10^{ - 2} \left( {\rm torr} \right)^{ - {1 \mathord{\left/ {\vphantom {1 2}} \right. \kern-\nulldelimiterspace} 2}} {\rm s}^{ - 1}$\end{document} for the isospecific ones and \documentclass{article}\pagestyle{empty}\begin{document}$ k_{p,a} = 58 \left( M {\rm s} \right)^{ - 1} ,k_{tr,a}^{\rm A} = 3 \times 10^{ - 3} {\rm s}^{ -1}$\end{document} for the nonspecific sites. Catalyst of VCl3 supported on MgCl2 has comparable productivity as the VCl4/MgCl2 catalyst but catalyst of VCl2 supported on MgCl2 exhibit only one‐ninth of the productivity. Extensive comparison has been made between the CW–V and the CW–Ti systems which revealed striking similarities between their polymerization behaviors. MgCl2 exerts profound influence on the stereochemical control of the vanadium ion on its activity for monomer coordination and insertion.