This work presents an electronic nose (EN)-based gas identification and concentration estimation method for the detection of food spoilage. The response data of sensors were acquired through a commercial gas sensor array and data acquisition circuit board and transformed into pictures with the form of the Fourier series. A convolutional neural network (CNN) model was used to identify the pictures from the conversion of sensor data, thus achieving the purpose of identifying the gases (C 2 H 5 OH, NH 3 , and H 2 S). In order to solve the problem of sample imbalance and to improve the generalization performance of classification models, the synthetic minority oversampling technique (SMOTE) and dropout technique were employed. Fivefold cross-validation was used to evaluate the performance of the model, of which the gas identification accuracy rate reached 96.67%. Moreover, a gas concentration regression model with the advantages of simplicity and strong interpretability was further proposed to estimate the concentrations of C 2 H 5 OH, NH 3 , and H 2 S. The mean absolute errors and coefficients of determination for the concentration estimation of C 2 H 5 OH, NH 3 , and H 2 S are (3.71 ppm, 0.968), (0.50 ppm, 0.968), and (0.13 ppm, 0.99), respectively. Furthermore, we used our model to evaluate the freshness of kiwifruit, pork, and beef, and it showed satisfactory predictive performance. The method proposed in this work realizes high-precision detection of gases from food spoilage and has a good application prospect in the rapid judgment of food freshness on the EN system.