<p><strong>Abstract.</strong> Megacities are major sources of anthropogenic fossil fuel CO<sub>2</sub> emissions. The spatial extents of these large urban systems cover areas of 10,000 km<sup>2</sup> or more with complex topography and changing landscapes. We present a high-resolution land-atmosphere modelling system for urban CO<sub>2</sub> emissions over the Los Angeles (LA) megacity area. The Weather Research and Forecasting (WRF)-Chem model was coupled to a very high-resolution FFCO<sub>2</sub> emission product, Hestia-LA, to simulate atmospheric CO<sub>2</sub> concentrations across the LA megacity at spatial resolutions as fine as ~ 1 km. We evaluated multiple WRF configurations, selecting one that minimized errors in wind speed, wind direction, and boundary layer height as validated by its performance against meteorological data collected during the CalNex-LA campaign (May&#8211;June 2010). Our results show no significant difference between moderate- (4-km) and high- (1.3-km) resolution simulations when evaluated against surface meteorological data, but the high-resolution configurations better resolved PBL heights and vertical gradients in the horizontal mean winds. We coupled our WRF configuration with the Vulcan 2.2 (10 km resolution) and Hestia-LA (1.3-km resolution) fossil fuel CO<sub>2</sub> emission products to evaluate the impact of the spatial resolution of the CO<sub>2</sub> emission products and the meteorological transport model on the representation of spatiotemporal variability in simulated atmospheric CO<sub>2</sub> concentrations. We find that high spatial resolution in the fossil fuel CO<sub>2</sub> emissions is more important than in the atmospheric model to capture CO<sub>2</sub> concentration variability across the LA megacity. Finally, we present a novel approach that employs simultaneous correlations of the simulated atmospheric CO<sub>2</sub> fields to qualitatively evaluate greenhouse gas measurements over the LA megacity. Spatial correlations in the atmospheric CO<sub>2</sub> fields reflect the coverage of individual measurement sites when a statistically significant number of sites observe emissions from a specific source or location. We conclude that elevated atmospheric CO<sub>2</sub> concentrations over the LA megacity are composed of multiple fine-scale plumes rather than a single homogenous urban dome. Furthermore, we conclude that FFCO<sub>2</sub> emissions monitoring in the LA megacity requires FFCO<sub>2</sub> emissions modelling with ~ 1 km resolution since coarser resolution emissions modelling tends to overestimate the observational constraints on the emissions estimates.</p>