New bimetallic catalysts based on microspherical TiCl3 modified with vanadium trichloride to obtain its different concentrations on the TiCl3 surface were synthesized. The presence of a VCl3 crystalline phase in the catalyst was confirmed by X-ray analysis. The synthesized catalysts were applied to studying propylene polymerization in a liquid monomer medium. The kinetics of the polymerization process was determined, and the structure and properties of the synthesized isotactic polypropylene (IPP) were established. It was demonstrated that the PPI samples synthesized over the developed titanium–vanadium catalysts has enhanced freeze resistance as compared to IPP sample obtained over conventional titanium catalysts.