Telechelic polystyrenes with five benzyl chloride moieties at the polymer end (PSt-E) were prepared by coupling reaction of polystyryllithium with hexakis(4-chloromethylphenoxy)cyclotriphosphazene (4). The coupling reaction occurs almost quantitatively and unfavorable side reactions were not operative. When a mole ratio [4]/[sec-BuLi]=9.3 was used, polystyrenes with cyclophosphazene carrying five benzyl chloride moieties at the polymer end (PSt-E) were obtained in more than 90% yield, which have narrow and predictable molecular weights (<(M)over bar (w)>/<(M)over bar (n)>=1.05). A star shaped polystyrene with phosphazene core could also be prepared by using excess polystyryl anions.