Land surface temperature (LST) is an important parameter for mirroring the water–heat exchange and balance on the Earth’s surface. Passive microwave (PMW) LST can make up for the lack of thermal infrared (TIR) LST caused by cloud contamination, but its resolution is relatively low. In this study, we developed a TIR and PWM LST fusion method on based the random forest (RF) machine learning algorithm to obtain the all-weather LST with high spatial resolution. Since LST is closely related to land cover (LC) types, terrain, vegetation conditions, moisture condition, and solar radiation, these variables were selected as candidate auxiliary variables to establish the best model to obtain the fusion results of mainland China during 2010. In general, the fusion LST had higher spatial integrity than the MODIS LST and higher accuracy than downscaled AMSR-E LST. Additionally, the magnitude of LST data in the fusion results was consistent with the general spatiotemporal variations of LST. Compared with in situ observations, the RMSE of clear-sky fused LST and cloudy-sky fused LST were 2.12–4.50 K and 3.45–4.89 K, respectively. Combining the RF method and the DINEOF method, a complete all-weather LST with a spatial resolution of 0.01° can be obtained.