Partial oxidation of methanol to formaldehyde on silver catalyst represents an important industrial process due to the versatility of formaldehyde as an intermediate in chemical synthesis. The development of kinetic models is essential for a quantitative description of the changes in concentration of the chemical species involved in the process due to reaction as well as for process design and optimisation purposes. Microreactor platforms represent effective tools for the quick development of reliable kinetic models. However, the development and identification of kinetic models is strictly related to the execution of informative experiments, allowing either elucidation of the complex reaction pathways involved in the oxidation process or providing a precise estimation of the kinetic parameters for each candidate model. In this work a model-based design of experiments (MBDoE) procedure is proposed where experiments are optimally designed for both discriminating among competing models and for improving the estimation of kinetic parameters. The proposed methodology allows the most influential reaction pathways to be elucidated and provides a sequence of optimally informative experiments showing the key role of temperature in the kinetic model identification procedure