Pentamethylcyclopentadienyltitanium trichloride, bis(cyclopentadienyl)titanium dichloride ($Cp_2TiCl_2$), and bis(pentamethylcyclopentadienyl)titanium dichloride were used in the polymerization of styrene without the aid of Group I-III cocatalysts. The properties of the resulting polymer indicated that polymerization was more controlled than in thermal polymerization. The kinetic studies indicated that a lower level of termination is present and that the polymer chain can be extended by adding an additional monomer. To elucidate the mechanism of polymerization, a series of experiments was performed. All results supported the involvement of a radical mechanism in the polymerization using $Cp_2TiCl_2$. The possibility of atom transfer radical polymerization (ATRP) mechanism was investigated by isolating the intermediate species. We could confirm the activation step from the reaction of 1-PEC1 with $Cp_2TiCl$ by detecting the coupling product of the generated active radicals. However, the reversible deactivation reaction competes with other side reactions, and it detection was difficult with our model system.