Municipal district adjustment and built-up area expansion are two main forms of urban spatial expansion. Using geometric methods, this study constructed a space-time path method to characterize the space-time relationship between municipal district adjustment and built-up area expansion, and drew the space-time path sets of major prefecture level cities from 2000 to 2010 by constructing a coordinate system of the standardized built-up areas and municipal district areas. This divided them into four quadrants, namely, H-H, L-H, L-L, and H-L, based on the relative mean value to evaluate overall and individual stability by three indexes of the trajectory vectors, namely, direction, length, and slope. Results provide the following conclusions. 1) Municipal district adjustment is an effective spatial expansion way for city-scale promotion in China. Since 2000, municipal district adjustments have been mainly distributed in the eastern coastal regions and mid-western capital cities along with their surrounding cities. 2) Municipal district adjustment affects the scale and status of a city in China. Many cities that have expanded municipal districts behave stably and cross quadrants. 3) Great majority second-tier cities have effectively promoted their scale and status through municipal district adjustment. The municipal district adjustment of medium and small cities in the mid-west area is relatively advanced compared with city development. 4) Municipal district adjustment with minimal magnitude is severely restricted from upgrading the scale and status of a city. The transformation from entirely incorporated counties or cities to municipal districts should be the mainstream in future municipal district adjustment.