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Rooftop photovoltaics (RPVs) are crucial in achieving energy transition and climate goals, especially in cities with high building density and substantial energy consumption. Estimating RPV carbon mitigation potential at the city level of an entire large country is challenging given difficulties in assessing rooftop area. Here, using multi-source heterogeneous geospatial data and machine learning regression, we identify a total of 65,962 km2 rooftop area in 2020 for 354 Chinese cities, which represents 4 billion tons of carbon mitigation under ideal assumptions. Considering urban land expansion and power mix transformation, the potential remains at 3-4 billion tons in 2030, when China plans to reach its carbon peak. However, most cities have exploited less than 1% of their potential. We provide analysis of geographical endowment to better support future practice. Our study provides critical insights for targeted RPV development in China and can serve as a foundation for similar work in other countries.