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Rapid urbanization has significant effects on China's CO2 emissions and contributes to climate change. Using a cross city panel of 64 cities from four large urban agglomerations in China over 2006-2013, we estimate urban household residential energy-related CO2 emissions. We then apply fixed effects two stage least squares (2SLS) to explore the relationship between urbanization and residential CO2 emissions, using an augmented Stochastic Impacts by Regression on Population, Affluence and Technology (STIRPAT) model. The results show that the average amount of residential CO2 emissions in these four agglomerations has a strong increasing trend over 2006-2013, rising from 2.85 to 5.67 million tons (Mt). Those with municipality and capital city status emit more residential CO2 emissions. A rising urban population share significantly influences residential CO2 emissions, as does population scale, GDP per capita, urban compactness and the comprehensive level of urbanization. Urban population share has positive effects on residential CO2 emissions even pasting the demarcation point (75%) in China's urban agglomerations. GDP growth has negative effects on residential CO2 emissions. Therefore, urban agglomerations' development and expansion should be designed to be well-organized. Policy makers should pay more attention to the urbanization patterns and design a guide for green development and sustainable lifestyle in the process of China's eco-urbanization. (C) 2018 Elsevier Ltd. All rights reserved.