H-ZSM-5 catalyst powders before and after a steaming post-treatment have been investigated during the Methanol-To-Hydrocarbons (MTH) process at 350 °C. Bulk and surface characterization techniques have been combined with in situ Scanning Transmission X-ray Microscopy (STXM) at the aluminum and carbon K-edge to study the changes in acidity, porosity, reactivity, and aluminum distribution upon steaming. It was found that steaming post-treatment has a positive impact on the stability of H-ZSM-5 without inducing important changes in the MTH activity and selectivity. The lower MTH stability of non-steamed H-ZSM-5 catalyst powder is related to the formation of poly-aromatic compounds in the outer regions of the catalyst particles, as probed with in situ STXM. In contrast, a limited amount of poly-aromatics was found in the outer rim of steamed H-ZSM-5 catalyst particles. These differences occur as a result of the generation of mesoporosity as well as the reduction in the number and strength of acid sites after steaming, as evidenced by the nanoscale imaging of adsorbed pyridine with STXM.