As one of the main grain crops in China, maize is highly susceptible to Aspergillus infection during processing, storage and transportation due to high moisture at harvest, which results in the loss of quality. The aim of this study is to explore the early warning marker molecules when Aspergillus infects maize kernels. Firstly, strains MA and MB were isolated from moldy maize and identified by morphological characterization and 18S rRNA gene sequence analysis to be Aspergillus flavus (A. flavus) and Aspergillus niger (A. niger). Next, fresh maize was moldy by contaminated with strains MA and MB. The volatile organic compounds (VOCs) during the contamination process of two fungal strains were analyzed by gas chromatography-ion mobility spectrometry (GC-IMS). A total of 31 VOCs were detected in maize contaminated with strain MA, a total of 32 VOCs were detected in maize contaminated with strain MB, including confirmed monomers and dimers. Finally, heat maps and principal component analysis (PCA) showed that VOCs produced in different growth stages of Aspergillus had great differences. Combined with the results of GC-IMS, total fungal colony counts and fungal spores, it was concluded that the Aspergillus-contaminated maize was in the early stage of mold at 18 h. Therefore, the characteristic VOCs butan-2-one, ethyl acetate-D, Benzaldehyde, and pentan-2-one produced by maize at 18 h of storage can be used as early mildew biomarkers of Aspergillus infection in maize. This study provided effective marker molecules for the development of an early warning and monitoring system for the degree of maize mildew in granaries.