The reaction of methylhydroquinone with hexachlorocyclotriphosphazene in the presence of a base, 4-picoline, in cyclohexane was investigated. Nuclear magnetic resonance spectroscopy, multiangle laser light scattering, and elemental analyses were performed on the product and two other related phosphazene materials produced by analogous synthetic routes: poly[hexakis(4-hydroxyphenoxy)cyclotriphosphazene] (1) and hexakis[(3-tert-butyl)(4-hydroxyphenoxy)]cyclotriphosphazene (2). Unlike the data for 2 where the tert-butyl moiety enforced regiospecific nucleophilic addition, the data for the methylhydroquinone-substituted cyclotriphosphazene product indicate that the less sterically bulky methyl group provides only limited protection for the adjacent hydroxyl group. The result is the formation of a low molecular weight oligomer, poly(hexakis[(methyl)(4-hydroxyphenoxy)]cyclotriphosphazene) (3), instead of a discrete cyclic trimer species.