The study of land use efficiency (LUE) evaluation and coupled coordination (CC) relationships under the perspective of urbanization can reasonably allocate land resources and contribute to the solution for agriculture, rural areas, and farmers. The LUE evaluation index system is constructed in three aspects: economy, society, and ecology. Then the LUE and CC degrees of Yunnan Province from 2010 to 2020 are measured, and the characteristics of LUE and the relationship of CC in each administrative region at each level are analyzed in space. Besides, the overall LUE and CC relationship in Yunnan Province is described. The study concludes that (1) The urbanization process in Yunnan Province is accelerating, unused land is decreasing, and construction land is increasing. (2) During the study period, the LUE of Kunming was much higher than that of other regions. The economic efficiency of the inner circle cities centered on Kunming is higher, while the economic efficiency of the outer circle cities is lower; social efficiency is increasing year by year except for Nujiang and Diqing, showing a higher pattern in the east than in the west; ecological efficiency is not increasing year by year except for Kunming, Qujing, and Lijiang, showing a higher pattern in the east than in the west; comprehensive efficiency is on the rise, with Kunming and Qujing leading the way with the overall pattern of “east > central > west.” The high-value area is relatively stable, and the low-value area has a clear tendency to shift eastward. (3) The coupling level of economic, social, and ecological efficiency of land use in administrative regions of Yunnan Province is low, but the coupling relationship is gradually optimized, showing the “contiguous effect” and realizing the state of extreme disorder to severe disorder in a large area. (4) The overall CC of three subsystems in Yunnan Province shows a fluctuating upward trend; the comprehensive efficiency index has an upward trend except for a slight decrease in 2017–2018; from 2010 to 2019, ecological and social efficiency is better than economic efficiency.