The compatibility of polyphosphazene (PPZ) polymer electrolytes with MnO2/C/SPE intercalation cathodes (IC) was investigated. Three-layered laminates of a phosphazene-based solid polymer electrolyte (SPE) film sandwiched between two MnO2-based ICs (one preloaded with lithium) were constructed. The cathodes were fabricated by either solvent casting or compression techniques. Two different crystal forms of manganese(IV) oxide—λ-MnO2 and γ-MnO2—were employed, together with methoxy ethoxy ethoxy PPZ (MEEP) SPE binder material. Carbon black was employed as the electronically conductive phase. One cathode in each laminate was prepared in the ‘chemically intercalated’ form by using LiMn2O4 in place of MnO2. The podand polymer, SMEP, which has better thin film mechanical properties than does MEEP, was complexed with lithium trifluoromethane sulfonate (Li triflate) and used as the SPE. Li+ ions were cycled galvanostatically between the two-ICs, through the phosphazene-based SPE layer. The performance of the cell was continuously monitored by electrochemical impedance spectroscopy (EIS) and by measuring the laminate thickness and voltage drop. The method of cathode fabrication (casting vs. pressing) was found to be the primary factor influencing the cycle life.