As an effective indicator of urbanization, impervious surfaces play a significant role in urban planning and ecological protection. It is, therefore, important to characterize impervious surfaces in urban geographical studies. As a key city in East China, Xuzhou has experienced rapid urbanization in recent decades and is now becoming an environmentally friendly city. To better understand the spatiotemporal heterogeneity of Xuzhou’s urban development, we extracted its impervious surfaces from Landsat images of 1995, 2003, 2010, and 2018 by a linear spectral mixture analysis. Then, a range of complementary methods including landscape indices, profile lines, median centers, standard deviational ellipses, and spatial autocorrelation were adopted to analyze the landscape pattern and expansion of impervious surfaces on both city and district scales. Results show that (1) there was a constant impervious surface expansion, originating in downtown Xuzhou; (2) promoting ecological protection in urban areas fragmented impervious surfaces with increasing heterogeneity and diversity overall; and (3) expansion directions and rates of impervious surfaces varied with district and town, and the central urban area expanded towards east and southeast, which could be related to their own resources and governmental policies. Findings from this study provide useful insights into urban planning of this economically prospective region.