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Global warming caused by massive carbon emissions poses a serious threat to the environment and human beings. Dynamic monitoring of the spatio-temporal evolution of carbon emissions is an essential way to achieve carbon reduction goals, especially in coastal areas like Guangdong Province faced with dual challenges of massive carbon emissions and rigorous reduction targets. To reveal the spatio-temporal characteristics of carbon emissions and provide a basis for further fine-grained carbon emission reduction strategies, we analyzed spatio-temporal distribution characteristics of carbon emissions in Guangdong Province at the county-level scale from 2000 to 2020. Based on the land-use data obtained from the Data Center for Resources and Environmental Sciences of the Chinese Academy of Sciences and energy consumption data from the Statistical Yearbook, the carbon emission of each county is estimated, and the spatio-temporal evolutionary features of them are explored by a series of methods of the exploratory spatio-temporal data analysis (ESTDA). The shift of spatial distribution characteristics and gravity center is further revealed with the standard deviational ellipse and gravity center migration analysis.The results reveal that the net carbon emissions increased from 6179.229 × 104 tons to 20765.723 × 104 tons during 2000–2020. The net carbon emissions of county-level administrative regions show a significant positive spatial correlation, and the spatial convergence shows a trend of first decreasing and then increasing. The spatio-temporal pattern of carbon emissions has an obvious path dependence and locked spatial features, and shows a gradually strengthening trend. The spatial distribution of carbon emissions formed a stable “northeast-southwest” pattern, and the gravity center of carbon emissions in the past 20 years has been distributed between 113.208°–113.357°E and 22.760°–22.878°N, tending slightly shifting to the northeast. The results of the study can help understand the spatio-temporal evolution of carbon emissions in Guangdong, and provide a reference for formulating effective carbon reduction policies.