In the high-level radioactive waste disposal repository, bentonite is a preferred buffer material. As the buffer material, the hydraulic conductivity must be less than 10−13 m/s and the thermal conductivity should be higher than 0.8 W/(m·K) recommended by International Atomic Energy Agency (IAEA). Due to the decay heat of radionuclide and low thermal conductivity of bentonite, the released heat cannot be quickly transferred to the host rock through bentonite buffer layer and the repository may be in a high temperature state (>100 °C), which compromises both the hydro-mechanical performance of the bentonite and the anti-corrosion behavior of nuclear waste canister, therefore the barrier function of the buffer layer is severely damaged. Thus, a double-layered buffer concept which is based on the dual requirements of thermal conductivity and permeability was proposed for the nuclear waste disposal repository. In this paper, coupled thermal-hydro model tests of double-layered buffer with graphite-bentonite mixture layer and bentonite layer (the layer thickness ratio of graphite-bentonite to bentonite was 2:3) were carried out to investigate the temperature and relative humidity distribution laws and determine whether the physicochemical properties of double-layered buffer change after experiencing the coupled thermal-hydro process. In the model test, a heater simulating the decay heat generated by HLW was placed below the graphite-bentonite layer, and a hydration system simulating groundwater infiltration was installed above the bentonite layer, thus, the heat was transferred from the graphite-bentonite layer to the bentonite layer while water was permeated from the bentonite layer to the graphite-bentonite layer. The temperature and relative humidity distribution were synchronously measured by temperature-humidity sensors. After the model tests, the heater was switched off, and the tested bentonite/graphite-bentonite mixture samples were taken out for subsequent water content, scanning electron microscopy (SEM) and X-ray diffraction (XRD) tests. The main conclusions from the test results are as follows. The distributions of temperature and relative humidity in the buffers were mainly governed by the competition between the thermal effect and the water permeation effect, the results of water content at different distances also indirectly verify this conclusion. And SEM results showed that macropores of the bentonite close to the water inlet side were significantly reduced and the pore distribution tended to be uniform along the water injection direction during wetting. XRD results indicated that the mineral composition of the graphite-bentonite mixtures close to the heater changed while that of the bentonite away from the heater remained unchanged. Obviously, even if the high thermal conductivity graphite was added to the buffer layer near the heat source, the mineral composition of the bentonite at the heat source side cannot be avoided completely unaffected. Therefore, it is necessary to conduct heat from the inner layer to outer layer to reduce the overall temperature in the repository and reduce adverse effects of temperature and water synchronization on outer bentonite layer. The research results in this paper can serve as a guideline for the buffer layer design in the high-level radioactive waste repository.