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The physicochemical properties of (1 − x)CsH2PO4/ xSiP y O z ( x = 0.2–0.7) composites containing fine-particle silicon phosphates as heterogeneous additives have been studied at different humidities. The introduction of silicon phosphates suppresses the superionic phase transition of CsH2PO4 and increases the low-temperature conductivity of the materials, which depends significantly on humidity. The CsH2PO4-SiP y O z materials offer high conductivity (∼3 × 10−3 to 10−2 S/cm at ∼110–230°C) at low water vapor pressures (3 mol % H2O). Amorphization of the CsH2PO4 in the composites markedly changes its thermodynamic properties. The effect of long-term isothermal holding (210°C, 3 mol % H2O) on the conductivity of the composites has been studied. [ABSTRACT FROM AUTHOR]