Highly porous, crystalline zeolite catalysts are used industrially to catalyze the conversion of methanol to gasoline. We have performed a picosecond spectroscopic study providing insights into both the structure and the dynamics of methanol adsorbed to acid zeolites. We reveal the adsorption structure of methanol at the catalytically reactive site and show that the reaction of this complex in the zeolite to the first intermediate in the methanol-to-gasoline reaction sequence is initiated by picosecond infrared excitation. The picosecond dynamics of this activation process can be followed in real-time, and reflects the potential energy surface relevant to the reaction.