Using time-series VIIRS nighttime light imagery, this paper studies the urbanization development of Guizhou Province from 2012 to 2019 by measuring the total amount of nighttime light, using the rank scale rule and the law of the primate city as well as extracting the lighted area. The results show that the total amount of nighttime light in all cities of Guizhou Province shows a growth trend. In addition, the growth rates of nighttime light in Liupanshui, Qianxinan and Guiyang are far lower than other cities. Zunyi maintains the fastest growth in the province on the basis of large amount of light. The development vitality of small and mediumsized cities is better than that of the biggest city. The urban structure is scattered. The biggest city has weak agglomeration effect and does not fully play its leading role. With the high growth trend of the second city (Zunyi City), the law of the primate city is gradually decreasing, and Guizhou Province has a trend of bipolar growth.