In the present work CpTiCl3 pretreated with tri-iso-butylaluminium was immobilized on MgCl2 supported Ziegler-Natta catalyst. The resulting catalysts were characterized by a series of techniques, namely thermal analysis (TGA/DTA), X-ray photoelectron spectroscopy (XpS), Al-27 magic angle spin nuclear magnetic resonance (Al-27 MAS-NMR), UV-VIS spectroscopic analysis, inductively-coupled plasma-atomic emission spectroscopy (ICP-AES) and elemental analysis. The catalysts UV-VIS spectrum showed a broad absorption band at 390 nm indicating the presence of metallocene cyclopentadienyl ring. According to XPS analysis, only hybrid catalysts showed two peaks in the Ti (2p(3/2)) region after the spectrum deconvolution, a lower binding energy peak at 455 eV and another one at 457 eV (Ti4+). These appear to be due to difference of electronegativity, in the coordination sphere of the Ti due to the TiCl4 and the Cp(i-Bu)TiCl2, fixed on the hybrid Ziegler-Natta catalyst. All catalyst systems were active in ethylene-1-butene copolymerization. The resulting polymers obtained with the hybrid catalyst showed a shoulder in the DSC thermogramme fusion peak. It might be caused by a polymer fraction produced by the additional Ti center in the catalyst due to the Cp(i-Bu)TiCl2. Microscopic analysis showed that the polymer replicated the spherical morphology of the catalyst grain.