Textile‐based generators that can convert low‐grade energy from the human body or environment into sustainable electricity have generated immense scientific interest in self‐powered wearable applications. However, their low power density and environmental suitability have extremely restricted their portable applications in complex and mutable environments. Herein, an asymmetric sandwich structure between molybdenum disulfide (MoS2)‐carbonized silks (MCs) and MoS2/MXene–Cottons (MMCs) to construct efficient thermo–hydroelectric generators (THEGs) that synergistically harvest heat‐moisture energy to generate considerable electricity is rationally designed. Notably, the large surface area of MoS2/MXene van der Waals heterojunctions (vdWhs) enables efficient charge collection, and the vertical MoS2 nanosheet arrays supply abundant nanochannels for a highly efficient hydration effect, generating an output power density of 32.26 µW cm−2 after wetting with deionized water. Combined with the sensitive temperature recognition ability with a Seebeck coefficient of 23.5 µV K−1, the application possibilities of these prepared THEGs in the mutual conversion of fingertip temperature/language, and the monitoring of the human physiological state is foresee. Thermo–hydroelectric generators (THEGs) are successfully constructed based on a sandwich structure between p‐type MoS2‐carbonized silks (MCs) with vertical MoS2 nanosheet arrays and n‐type MoS2/MXene–Cottons (MMCs) with van der Waals heterojunctions, demonstrating a Seebeck coefficient of 23.5 µV K−1 and a high output power density of 32.26 µW cm−2, which are favorable acting as self‐powered sensors for health monitoring.