Some of the seed-evolved volatiles, which were mainly composed of methanol, acetaldehyde, ethanol and acetone, caused the loss of seed germinability during storage. In general, the deleterious effects of the volatiles increased with increasing RH and temperature during storage. Acetaldehyde had the strongest deleterious effect regardless of RH and temperature, while ethanol caused seed deterioration only at high RHs. Acetone was slightly deleterious to some species, while methanol was almost inert in most seeds. Various aldehydes applied during storage showed some toxicity to seed germinability, which decreased, except for 3-methylbutanal, with increasing molecular size, suggesting that the endogenous volatile compounds with an aldehyde group cause seed deterioration. On the other hand, the contents of volatile compounds in seeds were higher when they were stored at 44% RH (water sorption zone 2), than when stored at 12% RH (water sorption zone 1). Acetaldehyde, the most deleterious volatile, was more abundantly accumulated within the seeds stored at −3.5°C than at 23°C. Based on these facts, it is suggested that endogenous volatiles, especially acetaldehyde, may be an important factor that accelerates seed deterioration which often occurs under lower RHs and/or temperatures throughout long-term storage.