New process developments linked to Power to X (energy storage or energy conversion to another form of energy) require tools to perform process monitoring. The main gases involved in these types of processes are H₂, CO, CH₄, and CO₂. Because of the non-selectivity of the sensors, a multi-sensor matrix has been built in this work based on commercial sensors having very different transduction principles, and, therefore, providing richer information. To treat the data provided by the sensor array and extract gas mixture composition (nature and concentration), linear (Multi Linear Regression—Ordinary Least Square “MLR-OLS” and Multi Linear Regression—Partial Least Square “MLR-PLS”) and non-linear (Artificial Neural Network “ANN”) models have been built. The MLR-OLS model was disqualified during the training phase since it did not show good results even in the training phase, which could not lead to effective predictions during the validation phase. Then, the performances of MLR-PLS and ANN were evaluated with validation data. Good concentration predictions were obtained in both cases for all the involved analytes. However, in the case of methane, better prediction performances were obtained with ANN, which is consistent with the fact that the MOX sensor’s response to CH₄ is logarithmic, whereas only linear sensor responses were obtained for the other analytes. Finally, prediction tests performed on one-year aged sensor platforms revealed that PLS model predictions on aged platforms mainly suffered from concentration offsets and that ANN predictions mainly suffered from a drop of sensitivity.