A systematic investigation of two sets of defect free and defective ZSM-5 crystals with controlled thickness (T) between 30 and 400 nm and of their performances in methanol conversion was reported for the first time in the present work. The defect free ZSM-5 crystals with a thickness of 35 nm are by far the smallest ever reported and displayed superior activity, stability and selectivity to slower diffusing compounds, which resulted in high yield of e.g. gasoline and the 1,2,4-trimethylbenzene isomer with high octane number, as compared to the other studied catalysts. Almost only products forming in the zeolite pores were detected and consequently, the external surface must be nearly inactive. Strong correlations between T and deactivation rate were observed. Thick crystals deactivated much faster than thin crystals, probably due to formation of carbon species in the zeolite pores, which results in pronounced percolation effects and faster deactivation of the former. At comparable thickness, crystals with defects deactivated much faster than defect free crystals, due to formation of additional small molecular coke species in the former. Strong correlations between T and selectivity were also observed and assigned to control of diffusion resistance by crystal thickness. © 2022 The Authors