The chemical composition of volatile organic compounds (VOCs) in landfill gas from municipal waste (MW) landfills primarily depends on the type of degrading waste. To provide first insights into the relationship between VOC chemistry (in landfill gas) and specific waste components, a lab-scale experiment on anaerobic digestion (AD) of green waste (GW) was carried out. The composition of the released C4+ VOCs was semi-quantitatively determined and indirectly compared to that generally expected for the overall MW landfill gas. The generated biogas from degrading GW during AD time showed up to 29 different VOCs, mainly including terpenes, followed by alkanes, alkenes, cyclics, aromatics, and halogenated compounds. O- and S-substituted compounds were sporadically detected. Overall, speciation and total concentration of VOCs fluctuated over AD time, likely due to changes in microbial populations and metabolism, as well as substrate depletion, during the AD evolution. As expected, VOC speciation in the GW biogas was lower than that of the typical MW landfill gas, since the latter is generated by a large variety of organic and synthetic waste components following different sequential degradation processes. These results highlighted that, when disposed of at MW landfill sites, the specific GW component may (i) potentially concur to the overall odour charge and toxic effects of MW landfill gas and (ii) detrimentally impact the energy exploitation of MW landfill gas by releasing terpenes, aromatics, and halogenated compounds.