The polymer [NPCl2](n) reacts with the functionalized biphenols bis(2-hydroxy-5-chlorophenyl)-methane [(HOC6H3Cl)(2)CH2], bis(2-hydroxyphenyl) ketone [(HOC6H4)(2)CO], and [racemic(+/-)], [R(+)]-, or [S(-)]-1,1＇-binaphthyl-2-ol [(HOC10H6C10H6OH)] (binaphthol), in THF, or 1,4-dioxane in the presence of K2CO3 or Cs2CO3 to give respectively the spirocyclic phosphazene homopolymers [NP(O2C13H8Cl2)](n) (1), [NP(O3C13H8)](n) (2), (+/-)-[NP(O2C20H12)](n) (5), (-)-[NP(O2C20H12)](n) [(-)-5b], and (+)-[NP(O2C20H12)](n) [(+)-5b], some of them also obtained as blends with poly(tetrahydrofuran). The reaction of [NPCl2](n) first with (HOC6H3Cl)(2)CH2 or (HOC6H4)(2)CO and subsequently with 2,2＇-biphenol ((HO)C6H4C6H4(OH)) in THF and in the presence of K2CO3 gave the random mixed copolymers [NP(O2C12H8)(0.6)(O2C13H8Cl2)(0.4)](n) (3) and [NP(O2C12H8)(0.6)(O3C13H8)(0.4)](n) (4) For comparison with the polymers, the two cyclic enantiomers (+)-[N3P3(O2C20H12)(3)] [(+)-6] and (-)-[N3P3(O2C20H12)(3)] [(-)-6] have been prepared from [N3P3Cl6] and [S(-)]-or [R(+)]-binaphthol, respectively, in acetone in the presence of Cs2CO3.