Volatile pollutants emitted from building materials are an important source of indoor air pollution. The development of rapid determination methods for the chemical concentration and odor concentration of these volatile pollutants is of great importance. The present work investigated the difference in the concentration of pollutants emitted by various paint samples, from which key pollutants (methyl isobutyl ketone, ethylbenzene, and xylene) were screened based on their concentration and odor contribution. Then, an electronic nose (E-nose) device was developed to determine the chemical concentrations of key pollutants and the odor concentration of gas emitted by paint samples. A total of 135 gas samples emitted by the selected paint were measured by the developed E-nose, by gas chromatography–mass spectrometry and by olfactory testing. The obtained sensor response values and chemical and odor concentrations were divided randomly and used for training and testing of the E-nose pattern recognition algorithm. The trained pattern recognition algorithm was able to accurately output the target values, with average relative errors of 10.0%, 10.4%, 7.6%, and 10.0% (test set, n = 13) for the methyl isobutyl ketone, ethylbenzene, and xylene chemical concentrations and the odor concentration, respectively. In addition, the cross-sensitive nature of the E-nose showed a unique advantage in determining odor concentration compared to the odor conversion model. The excellent performance of the developed E-nose demonstrates that this work provides a practical solution for the rapid determination of the chemical concentration and odor concentration of pollutants emitted by building materials.