A novel quantification technique is presented for electronic nose (E-nose), which is based on a double-step strategy combined with hierarchical classifier (HC) and partial least squares regression (PLSR). With the tree structure of HC, the complexity of classifier training process can be reduced in the case of unbalanced samples. For each level of the class hierarchy, the extreme learning machine-based artificial neural network (ELM-ANN) is applied for classification. In order to improve the classification performance of ELM-ANN, the multiple time-domain features are selected as training inputs, and a novel optimization method of the number of hidden layer neurons is given. To validate the effectiveness of the presented quantification technique, an E-nose system is designed to quantify the gases including six toxic gases (hydrogen sulfide, carbon monoxide, ammonia, toluene, formaldehyde, acetone) and three kinds of binary gas mixtures. This presented hierarchical classifier has demonstrated outstanding performance for the identification of target gases, such as the macro-averaged precision for unlabeled data is improved from 80% to 92% compared with non-hierarchical classifiers. Furthermore, an excellent performance of concentration estimation is obtained utilizing PLSR, where average values of the coefficient of determination for training and test samples are equal to 0.957 and 0.927, respectively. Overall, our work demonstrates that the proposed approach is applicable in E-nose-based odor quantification.