Plants are the major source of Biogenic Volatile Organic Compounds (BVOCs) which have a large influence on atmospheric chemistry and the climate system. Therefore, understanding of BVOC emissions from all abundant plant species at all developmental stages is very important. Nevertheless, investigations on BVOC emissions from even the most widespread agricultural crop species are rare and mainly confined to the healthy green leaves. Senescent leaves of grain crop species could be an important source of BVOCs as almost all the leaves senesce on the field before being harvested. For these reasons, BVOC emission measurements have been performed on maize (Zea mays L.), one of the most cultivated crop species in the world, at all the leaf developmental stages. The measurements were performed in controlled environmental conditions using dynamic enclosures and proton transfer reaction mass spectrometry (PTR-MS). The main compounds emitted by senescent maize leaves were methanol (31% of the total cumulative BVOC emission on a mass of compound basis) and acetic acid (30%), followed by acetaldehyde (11%), hexenals (9%) and m/z 59 compounds (acetone/propanal) (7%). Important differences were observed in the temporal emission profiles of the compounds, and both yellow leaves during chlorosis and dry brown leaves after chlorosis were identified as important senescence-related BVOC sources. Total cumulative BVOC emissions from senescent maize leaves were found to be among the highest for senescent Poaceae plant species. BVOC emission rates varied strongly among the different leaf developmental stages, and senescent leaves showed a larger diversity of emitted compounds than leaves at earlier stages. Methanol was the compound with the highest emissions for all the leaf developmental stages and the contribution from the young-growing, mature, and senescent stages to the total methanol emission by a typical maize leaf was 61, 13, and 26%, respectively. This study shows that BVOC emissions from senescent maize leaves cannot be neglected and further investigations in field conditions are recommended to further constrain the BVOC emissions from this important C4 crop species.