Lithium batteries utilizing solid-state electrolytes have the potential to alleviate their safety hazard, reduce packaging volume, and enable flexible design. Polymer/ceramic composite electrolytes (CPE) are more attractive because the combination is capable of remedying and/or transcending individual constituent’ properties. Recently, we fabricated a series of free-standing composite electrolyte membranes consisting of Li1.4Al0.4Ge1.6(PO4)3 (LAGP), polyethylene oxide (PEO), and lithium salts. In this study, we characterized thermal and mechanical properties of the CPEs with two representative lithium salts, i.e., lithium boron fluoride (LiBF4) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI). We found that the type of lithium salt can prevail the LAGP ceramic loadings on altering the key properties. It is observed that LiTFSI, compared with LiBF4, causes more significant reduction in terms of the crystallinity of PEO, melting transition, and mechanical strengths. The differences in these aspects can be ascribed to the interactions between the polymer matrix and anions in lithium salt.