This paper intends to examine the coupling and coordination degree (CCD) between the urbanization and ecological environment in Guizhou, China. The entropy weight method and coupling effect model were used to calculate the CCD between the urbanization and ecological environment of Guizhou and each of its prefectures. The results show the following: (1) there is an inverted U-shaped relationship between the urbanization and ecological environment deterioration in Guizhou, which can be described by the Kuznets curve; (2) both the urbanization and ecological environment improve with the increase in the CCD; (3) unlike the traditional urbanization path, the urbanization in Guizhou features the parallel progress of industrialization and ecological environment protection. These results prove another possibility of the Kuznets curve: the curve can reach the turning point without high urbanization. This new urbanization path of balance-upgrading provides an important reference for backward areas to realize low-carbon economy and sustainable development at the same time.