Polyethylenes and highly syndiotactic poly(propylene)s possessing chain end hydroxyl groups were synthesized by living polymerizations using L2TiCl2 [1, L: C6F5N=CH(2-O-C6H3-3-Bu-t)]MAO and functionalized alpha-olefins, H2C=CH(CH2)(n)-Y[2; Y=OAlMe2, n = 4 (2a); Y=OSiMe3, n = 9 (2b)]. Because the primary insertion of 2 to a cationic species L2Ti+-Me (3) derived from 1/MAO is much faster than the successive secondary insertion of 2, addition of an equimolar amount of 2 to 3 resulted in the quantitative formation of L2Ti+-CH2-CH(Me)-(CH2)(n)-Y [4; Y=OAlMe2, n = 4 (4a); Y=OSiMe3, n = 9 (4b)]. These cationic species 4 served as functionalized initiators for the living polymerization of both ethylene and propylene and afforded polyolefins having extremely narrow molecular weight distributions and a hydroxyl group at the initiating chain end. The terminating chain end of the syndiotactic poly(propylene)s was also functionalized by adding an excess amount of 2b as a chain end capping agent to the living L2Ti-polymeryl species. Due to much slower insertion of the second molecule of 2b relative to the first one, the obtained polymers were end capped quantitatively by a single molecule of 2b. Telechelic syndiotactic poly(propylene)s were successfully synthesized through a living polymerization initiated by 4b and an end capping using 2b.