Zeolite SSZ-39 is evaluated for catalyzing the methanol-to-olefins (MTO) reaction. By steaming NH4-SSZ-39, Al can be removed from framework positions, resulting in an increase in framework-Si/AlT and thus a lowered active acid site density. The Si/AlT ratios can be controlled by the steaming temperatures. SSZ-39 steamed at 750 °C, with preserved pore volume and morphology, is an excellent MTO catalyst, as high, stable olefin selectivities, long time-on-stream activity, and low alkane production are observed. Moreover, interesting propylene/ethylene/butylene ratios of 2.8/1/1.1 are obtained, likely related to the shape of the AEI cage. By Cu2+-exchanging SSZ-39, evidence is provided to show that AlT sites in close proximity (high AlT density) produce the unwanted effects (higher alkane-make and carbonaceous deposits) in nonsteamed materials during MTO.