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We discover superconductivity (SC) in LaAgSb at ambient pressure and its close correlation with a charge density wave (CDW) under pressure. The superconducting transition temperature () exhibits a sharp peak at the CDW critical pressure of 3.2 GPa. We demonstrate that the carriers inhabiting the Sb-square net is crucial not only in the formation of CDW but also in SC for their relatively strong electron-phonon coupling (EPC). Furthermore, theoretical EPC strength in pristine LaAgSb cannot explain the observed peak with K, which indicates that an additional mechanism reinforces SC only around the CDW critical pressure.

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