Natural iron-bearing sodic phonolitic melts represent an extreme compositional range of the effect of the [Na/(Na+K)] ratio on the geochemical behavior of Fe in volcanic systems. Yet phonolitic melts have not been well investigated. The glasses studied here have been synthesized from liquids equilibrated over a range of oxygen fugacity conditions [log10(fO2) from −0.68 to −11] to elucidate the role of the alkali ratio in influencing the local environment around both divalent and trivalent Fe. In this study, the Fe K-edge XAS spectra (XANES and EXAFS) have been employed, to constrain the Fe structural role (oxidation state, coordination number, bond distances) in phonolitic glasses as a function of synthesis temperature (T), [Na/(Na+K)] ratio (= 0.0, 0.25, 0.5, 0.75, 1.0) and redox state. We verify that at constant oxygen fugacity, the [Na/(Na+K)] ratio has a strong effect on the Fe3+/(Fe2++Fe3+) ratio. The results obtained are parameterized and discussed in terms of the contrasting effects of T, fO2, and alkali ratio.