Bioenergy crop production is rapidly expanding in Europe, and the potential emissions of biogenic volatile organic compounds (BVOCs) might change the chemical composition of the atmosphere, influencing in turn air quality and regional climate. The environmental impacts of bioenergy crops on air chemistry are difficult to assess due to a lack of accurate field observations. Therefore, we studied BVOC fluxes from a bioenergy maize field in North-Eastern Germany throughout the entire reproductive growth stage of the plants. Combining automated large chambers and proton transfer reaction mass spectrometry (PTR-MS), we successfully measured fluxes of the highly reactive hydrocarbons monoterpenes (MTs) and sesquiterpenes (SQTs), together with several other BVOCs, including alcohols, aldehydes, ketones, benzenoids, and fatty acid derivatives. Emissions of MTs and SQTs were relatively high (17.0% and 3.6% of total mean molar BVOC emission, respectively) compared to methanol emissions (17.6%). Seasonal MT and SQT fluxes were clearly associated with the flowering phase, originating mainly from the flowering tissues as shown in additional laboratory experiments. ... mehrFrom the observations of CO₂ net ecosystem exchange and evapotranspiration rates, we could exclude heat and drought stress-induced BVOC emissions. Standard emission factors calculated for all compounds, chemical groups, and growth stages, showed that the temperature dependency of volatile terpenoid fluxes decreased distinctively with proceeding development stage. The results indicate that emissions from large-scale bioenergy maize fields should be better differentiated and considered in regional estimates of aerosol formation. For the implementation of such relation into biogeochemical modelling, it should be considered that not only seasonal weather development but also phenological growth stages are determining the BVOC patterns and emission potentials.