The air void system purposely introduced by an air-entraining admixture (AEA) is of great significance for the protection of concrete from freeze–thaw damage. Fly ash has been globally used in concrete, while the unburnt carbon in fly ash can adsorb AEA molecules and, thus, increase the AEA demand. Previous studies primarily focused on the air content of fresh fly ash concrete. This paper aimed to explore the stability and distribution of air voids in fly ash concrete at the fresh state. To achieve this goal, eleven different fresh fly ash concrete mixtures with an initial air content of 6 ± 1% were prepared in the laboratory. Samples were taken at various times within 75 min after initial mixing to investigate the air content and air void distribution in fly ash concrete at the fresh state using a super air meter (SAM). The results indicated that there was no significant correlation between loss on ignition (LOI) of fly ash and AEA demand to achieve the initial air content of 6 ± 1%. Class C fly ash concrete tended to have a better air content retention than Class F fly ash concrete. Compared with LOI, AEA demand had a stronger correlation with air content retention. Most of the fly ash concrete mixtures had a satisfactory air void system immediately after mixing, but the SAM number showed an increasing trend over time, suggesting the coarsening of the air void system with time.