Titanium complexes having tridentate triamine of the type N[CH2CH(Ph)(Ts)N](2)(2-) in combination with methylaluminoxane (MAO) was able to polymerize ethyl vinyl ether in good yields. The polymers obtained in general were having molecular weight in the order of 10(5) with narrow molecular weight distributions. Polymerization conditions had an impact on the molecular weight and the polydispersity index (PDI). Using chlorobenzene as the solvent the polymer had an M-n of 350 000 and PDI of 1.21, where as under neat conditions the M-n was 255 000 with PDI of 1.21. The type of solvent and the temperature dictated the polymerization rate and the polymer stereo regularity. The molecular weight of the polymer is distinctly governed by the polymerization temperature. Temperature ranging between -50 and ambient (30 degrees C) resulted in high molecular weight polymers and vice versa at a temperature of 60-70 degrees C resulted in low molecular weight polymers in moderate yields. The polymers obtained below 30 degrees C are highly stereo-regular compared to that of the ones produced at and above ambient temperature. The polymerization of iso-butyl vinyl ether (IBVE) was faster than that of linearly substituted n-butyl vinyl ether (BVE) and less bulky ethyl vinyl ether (EVE). The order of isotacticities of the polymers obtained are polyIBVE > polyBVE > polyEVE. The use of borate cocatalyst for activation generated narrow molecular weight polymers with a linear increase in the yield and molecular weight over time suggesting the living nature of the catalyst system. Crown Copyright (C) 2008 Published by Elsevier Ltd. All rights reserved.