The upscaling of zeolitic materials to technical catalysts implies the formulation of the active phase with additives that can affect catalytic performance. As an alternative, we herein present fibrillar ZrO2/HZSM-5 composites prepared by electrospinning where HZSM-5 zeolite aggregates are joint through inert ZrO2 fibers. For zeolite loadings of 5, 10 and 20 wt% and SiO2/Al2O3 ratios of 30, 50 and 80, well-dispersed zeolite aggregates smaller than 1.5 μm have been observed. The ZrO2/HZSM-5 composites were tested as catalysts in the dimethyl ether-to-olefins (DTO) process. The maximum olefin selectivity (ca. 70%) but fastest deactivation was observed for a zeolite loading of 5 wt%, with side reaction extent being promoted when increasing zeolite loading or density of acid sites. A comparison with a technical catalyst suggested that secondary reactions are limited due to the homogeneous distribution of the zeolite in the fibrillary material and to the higher accessibility of zeolite crystals.