It is important to know how much of the increased atmospheric CO2 is derived from fossil fuel emissions. Here, we review the progress in atmospheric fossil fuel CO2 (CO2ff) tracing over recent years by measurement of Δ14C in Chinese cities. In this paper we make progress by expanding the analysis from some locations to more regional views, by combining observations with modeling, and by making a preliminary comparison of observation-derived CO2ff with inventory-derived CO2ff. We have obtained a general picture of Chinese urban CO2ff and characteristics of its spatio-temporal variations at different scale, and identified the corresponding influencing factors. Interestingly, we found that the weekend effect of CO2ff was less evident in Chinese cities. In addition, we observed simultaneous variations in CO2ff and PM2.5 in a winter haze event in Beijing and a simultaneous decrease in annual averages of CO2ff and PM2.5 in Xi’an based on multi-year (2011–2016) Δ14CO2 monitoring. We found that local coal combustion was the main source of CO2ff in Xi’an, which is located in the Guanzhong basin, by applying a WRF-Chem model and looking at δ13C signatures. Thus, reduction of coal consumption is a crucial target for carbon emissions reduction in China.