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The main components of landfill gas are methane and carbon dioxide. Emissions of methane, a strong greenhouse gas, can be minimized by in situ oxidation in the bioactive cover layer. Typically, organic-rich porous materials such as compost are used for this process. In this study, the material for a biocover was obtained from the same landfill by landfill mining. The objective was to study the spatial distribution of gases and the efficiency of methane degradation in the biocover. The methane and carbon dioxide emissions were measured at 29 measuring points six times on the surface and once at a depth of 0.5 m. The highest values of both gases from the surface were recorded in July 2015: 1.0% for CO2 and 2.1% for CH4. Deeper in the cover layer, higher values of methane concentration were recorded. The results showed that (a) methane from the waste deposit was entering the biocover, (b) the migration of methane to the atmosphere was low, (c) fluctuations in the composition of gases are seasonal, and (d) the trend in the concentration of CH4 over time was an overall decrease. The described cover design reduces the CH4 emissions in landfills using elements of circular economy—instead of wasting natural soils and synthetic liners for the construction of the final cover layer, functional waste-derived materials can be used.