This study investigates the concentration distribution of aldehydes and volatile organic compounds (VOCs) in the archive of the National Library in Korea and evaluates the health risks to workers from hazardous chemicals. Acetaldehyde had the highest concentration among the nine species of aldehydes present in the archive and the concentration of toluene was the highest among the six species of VOCs. Most of the detected substances showed that their indoor concentrations were higher than the outdoor ones, suggesting the possibility of indoor sources of aldehydes and VOCs. The evaluation of health risks for workers based on these measurement results showed that not all substances were hazardous to the human body. However, considering the possibility of the presence of indoor sources and the potential limits of our study owing its short period, it is necessary to conduct long-term studies on the concentration distribution of indoor pollutants in the archive environment.