The coordination polymerization of silyl-protected omega-alkenols such as omega-alken-alpha-oxytriisopropylsilanes 1 provides poly(omega-alkenyl-alpha-oxytriisopropylsilalne)s with a highly isospecific microstructure ([mmmm] > 95%) when a combination of [OSSO]-type bis(phenolato) dichloro zirconium(IV) complex 2 and dried methylaluminoxane is used as the precatalyst and activator, respectively. The resulting siloxy-substituted polymers could be efficiently transformed into the corresponding functionalized polyolefins, which contained up to 90% acetyl groups and approximate to 7% hydroxy groups in the terminal side chains.