Urbanized and industrialized areas are the largest source of fossil CO₂. This work analyses the atmospheric CO₂ variability observed from the first in situ network deployed in the Paris megacity area. Gradients of several ppm are found between the rural, peri-urban and urban sites at the diurnal to the seasonal scales. Wind direction and speed as well as boundary layer dynamics, correlated to highly variable urban emissions, are shown to be key regulator factors of the observed CO₂ records.