The combination of LiMn0.67Fe0.33PO4 positive and Li4Ti5O12 negative electrode is studied in terms of its entropy change behavior, which affects the reversible heat generation of a lithium-ion cell. This electrode combination is especially interesting for large applications, as it is proposed to be a very safe choice having still an adequate energy density. The entropy change of LiMn0.67Fe0.33PO4 and Li4Ti5O12 electrode materials is measured at different states of charge using a potentiometric method. The results are compared with conventional electrode materials, LiFePO4 and artificial graphite. The entropy change of LiMn0.67Fe0.33PO4 is found to follow the distinct plateaus of Fe2+/Fe3+ and Mn2+/Mn3+ redox couples and to be clearly different from LiFePO4. This difference is suggested to be due to single-phase solid solution regions, originating from effects of substituting Mn for Fe. For Li4Ti5O12, mostly a constant entropy change typical for a two-phase reaction is observed, except for the region near 0% state of charge. The data from individual electrodes is used to simulate and compare the entropy change behavior and thus the reversible heat generation rate of different electrode combinations.