Yunnan plays a pivotal role in transmitting electricity from west to east within China’s Southern Power Grid. During 7–13 January 2021, a large-scale continuous ice-covering event of ultra-high voltage (UHV) transmission lines occurred in the Qujing area of eastern Yunnan Province. Based on ERA5 reanalysis data and meteorological observation data of UHV transmission line icing in China’s Southern Power Grid, the synoptic causes of the icing are comprehensively analyzed from various perspectives, including weather situations, vertical stratification of temperature and humidity, local meteorological elements, and atmospheric circulation indices. The results indicate a strong East Asian trough and a blocking high directing northern airflow southward ahead of the ridge. Cold air enters the Qujing area and combines with warm and moist air from the subtropical high pressure of 50–110° E. As warm and cold air masses form a quasi-stationary front over the northern mountainous area of Qujing due to topographic uplift, the mechanism of “supercooling and warm rain” caused by the “warm–cold” temperature profile structure leads to freezing rain events. Large-scale circulation indices in the Siberian High, East Asian Trough, and 50–110° E Subtropical High regions provided clear precursor signals within 0–2 days before the icing events.