With the presence of highly permeable pathways, such as faults and fractures zones, coal seam gases, particularly CO₂, could potentially migrate upwardly from the coal deposits into the shallow subsurface and then to the atmosphere. This letter reports soil gas mapping and gamma ray survey in coal basin of Hunter River Valley, Australia. The survey facilitated the delineation of fault structures across the sampling regions, where the identified faults were confirmed by an independent drilling investigation later. Furthermore, to evaluate the gas emission fluxes from coalbeds through fault zones, the measured CO₂ concentrations, coupled with an inverse modeling, enable the estimation of the width of the fault zone and associated CO₂ emission flux in the range of 2 × 10−⁵–6 × 10−⁵ mol/m²/s at the study site. Our new approach provides a way to determine emissions of gases from deep formations, which may contribute considerably to the greenhouse gases cycles.