We employed an atmospheric transport model to attribute column‐averaged CO2 mixing ratios (XCO2) observed by Greenhouse gases Observing SATellite (GOSAT) to emissions due to large sources such as megacities and power plants. XCO2 enhancements estimated from observations were compared to model simulations implemented at the spatial resolution of the satellite observation footprint (0.1° × 0.1°). We found that the simulated XCO2 enhancements agree with the observed over several continental regions across the globe, for example, for North America with an observation to simulation ratio of 1.05 ± 0.38 (p < 0.1), but with a larger ratio over East Asia (1.22 ± 0.32; p < 0.05). The obtained observation‐model discrepancy (22%) for East Asia is comparable to the uncertainties in Chinese emission inventories (~15%) suggested by recent reports. Our results suggest that by increasing the number of observations around emission sources, satellite instruments like GOSAT can provide a tool for detecting biases in reported emission inventories.