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Nighttime light data play an important role in the research on cities, while the urban centers over a large spatial scale are still far from clearly understood. Aiming at the current challenges in monitoring the spatial structure of cities using nighttime light data, this paper proposes a new method for identifying urban centers for massive cities at the large spatial scale based on the brightness information captured by the Suomi National Polar-Orbiting Partnership's Visible Infrared Imaging Radiometer Suite (NPP-VIIRS) sensor. Based on the method for extracting the peak point based on digital elevation model (DEM) data in terrain analysis, the maximum neighborhood and difference algorithms were applied to the NPP-VIIRS data to extract the pixels with the peak nighttime light intensity to identify the potential locations of urban centers. The results show 7239 urban centers in 2200 cities in China in 2017, with an average of 3.3 urban centers per city. Approximately 68% of the cities had significant polycentric structures. The developed method in this paper is useful for identifying the urban centers and can provide the reference to the city planning and construction. [ABSTRACT FROM AUTHOR]