Carbon dioxide (CO2) and methane (CH4) are the two most important anthropogenic greenhouse gases. SCIAMACHY on ENVISAT is the first satellite instrument whose measurements are sensitive to concentration changes of the two gases at all altitude levels down to the Earth’s surface where the source/sink signals are largest. We have processed three years (2003–2005) of SCIAMACHY near infrared nadir measurements to simultaneously retrieve vertical columns of CO2 (from the 1.58μm absorption band), CH4 (1.66μm) and oxygen (O2 A-band at 0.76μm) using the scientific retrieval algorithm WFM-DOAS. We show that the latest version of WFM-DOAS, version 1.0, which is used for this study, has been significantly improved with respect to its accuracy compared to the previous versions while essentially maintaining its high processing speed (~1 min per orbit, corresponding to ~6000 single measurements, and per gas on a standard PC). The greenhouse gas columns are converted to dry air column-averaged mole fractions, denoted XCO2 (in ppm) and XCH4 (in ppb), by dividing the greenhouse gas columns by simultaneously retrieved dry air columns. For XCO2 dry air columns are obtained from the retrieved O2 columns. For XCH4 dry air columns are obtained from the retrieved CO2 columns because of better cancellation of light path related errors compared to using O2 columns retrieved from the spectrally distant O2 Aband. Here we focus on a discussion of the XCO2 data set. The XCH4 data set is discussed in a separate paper (Part 2). In order to assess the quality of the retrieved XCO2 we present comparisons with Fourier Transform Spectroscopy (FTS) XCO2 measurements at two northern hemispheric mid-latitude ground stations. To assess the quality globally, we present detailed comparisons with global XCO2 fields obtained from NOAA’s CO2 assimilation system CarbonTracker. For the Northern Hemisphere we find good agreement with the reference data for the CO2 seasonal cycle and the CO2 annual increase. For the Southern Hemisphere, where significantly less data are available for averaging compared to the Northern Hemisphere, the CO2 annual increase is also in good agreement with CarbonTracker but the amplitude and phase of the seasonal cycle show systematic differences (up to several ppm) arising partially from the O2 normalization most likely caused by unconsidered scattering effects due to subvisual cirrus clouds. The retrieved XCO2 regional pattern at monthly resolution over various regions show clear correlations with CarbonTracker but also significant differences. Typically the retrieved variability is about 4 ppm (1% of 380 ppm) higher but depending on time and location differences can reach or even exceed 8 ppm. Based on the error analysis and on the comparison with the reference data we conclude that the XCO2 data set can be characterized by a single measurement retrieval precision (random error) of 1–2%, a systematic low bias of about 1.5%, and by a relative accuracy of about 1–2% for monthly averages at a spatial resolution of about 7°×7 °. When averaging the SCIAMACHY XCO2 over all three years we find elevated CO2 over the highly populated region of western central Germany and parts of the Netherlands (“Rhine-Main area”) reasonably well correlated with EDGAR anthropogenic CO2 emissions. On average the regional enhancement is 2.7 ppm including an estimated contribution of 1–1.5 ppm due to aerosol related errors and sampling.