14C (radiocarbon) in atmospheric CO2 is the most direct tracer for the presence of fossil-fuel-derived CO2 (CO2-ff). We demonstrate the 14C measurement of wine ethanol as a way to determine the relative regional atmospheric CO2-ff concentration compared to a background site (“regional CO2-ff excess”) for specific harvest years. The carbon in wine ethanol is directly back traceable to the atmospheric CO2 that the plants assimilate. An important advantage of using wine is that the atmosphere can be monitored annually back in time. We have analyzed a total of 165 wines, mainly from harvest years 1990–1993 and 2003–2004, among which is a semicontinuous series (1973–2004) of wines from one vineyard in southwest Germany. The results show clear spatial and temporal variations in the regional CO2-ff excess values. We have compared our measured regional CO2-ff excess values of 2003 and 2004 with those simulated by the REgional MOdel (REMO). The model results show a bias of almost +3 parts per million (ppm) CO2-ff compared with those of the observations. The modeled differences between 2003 and 2004, however, which can be used as a measure for the variability in atmospheric mixing and transport processes, show good agreement with those of the observations all over Europe. Correcting for interannual variations using modeled data produces a regional CO2-ff excess signal that is potentially useful for the verification of trends in regional fossil fuel consumption. In this fashion, analyzing 14C from wine ethanol offers the possibility to observe fossil fuel emissions back in time on many places in Europe and elsewhere.