The identification of key VOCs during flights is important in creating a satisfactory aircraft cabin environment. Two VOC databases for the building indoor environment (from 251 occupied residences) and the aircraft cabin environment (from 56 commercial flights) were compared, to determine the common compounds (detection rate (DR) > 70%) in the two environments and the characteristic VOCs (only those with high DR during flights) in aircraft cabins. Possible VOC emission sources in flights were also discussed. As TVOC is usually viewed as a general indicator of air quality, the prediction of TVOC concentration was carried out using BP neural network algorithm, and the average error between the predicted and measured values was 55.35 μg/m³ (R² = 0.80). Meanwhile, the VOCs' inhalation cancer/non-cancer risks to crew members and passengers were calculated on the basis of detection rates, exposure concentrations, and health risk assessments. Six compounds (i.e., formaldehyde, benzene, tetrachloroethylene, trichloromethane, 1,2-dichloroethane, and naphthalene) were proposed as the key VOCs in the existing aircraft cabin environment, presenting a risk to crew members that is higher than the US EPA proposed acceptable level (evaluated mean value > 1E-06). The estimated lifetime excess cancer/non-cancer risks for passengers were all below the assessment criteria. Based on a summary of various VOC limits in five built environments, hierarchical design of VOC concentration limits is recommended for the aircraft environment.