Several small molecule cyclotriphosphazenes and high polymeric poly(organophosphazenes) with methylthio groups (CH3SR) have been synthesized: [NP(OCH2CH2SCH3)(2)](n) (n = 3, 1; n = 15,000, 5); [NP(OCH2CH2CH2CH2SCH3)(2)](n) (n = 3, 2; n = 15,000, 6); [NP(OCH2CH2CH(SCH3)CH2CH2CH3)(2)](n) (n = 3, 3; n = 15,000, 7); and [NP(OCH2C6H4SCH3)(2)](n) (n = 3, 4; n = 15,000, 8). Both series of compounds possess multiple thioether coordination sites for potential binding to metals. The methylthioethoxide substituent readily oxidizes to the sulfoxide derivatives in the presence of peroxides. All the phosphazenes were characterized by H-1-, C-13-, and P-31-NMR spectroscopy and elemental analysis, and the small molecule cyclotriphosphazenes were examined by mass spectrometry. Gel permeation chromatography (GPC) and differential scanning calorimetry (DSC) were also employed to characterize the polymers. Metal complexation and extraction capabilities of both the small molecule and polymeric systems are described.