AgSbTe2 plays a pivotal role in mid‐temperature thermoelectric generators (TEGs). Leveraging the seminal advances in cation manipulation within AgSbTe2, this study demonstrates an enhanced TE power factor (PF = S2σ) of 1.5 mWm−1 K−2 and a peak zT of 1.5 at 583 K in an off‐stoichiometric Ag1.04Sb0.96Te2 crystal. The introduction of Ge in place of Ag leads to an increased nH as evidenced by the detection of trace Ge4+ through XPS analysis. Further chemical state analysis reveals the simultaneous presence of Ag+, Sb3+, and Ge4+, elucidating the effect of cation modulations. TEM characterizations validate the presence of superlattice structure, and the linear defects discerned within the AgSbTe2 matrix. Consequently, the lattice thermal conductivity κL is substantially reduced in the Ag1.02Ge0.02Sb0.96Te2 crystal, yielding a peak zT of 1.77 at 623 K. This notable advancement is attributed to the counterbalance achieved between the enhanced PF and the reduced κL, facilitated by cation modulation. Additionally, a single‐leg TE device incorporating Ag1.02Ge0.02Sb0.96Te2 demonstrates a conversion efficiency of 7% across a temperature gradient (ΔT) of 350 K. This study corroborates the efficacy of cation modulation through thermodynamic approaches and establishes a relationship between transport properties and the presence of defects.