Hierarchical ZSM-5 zeolite can be obtained in a one-step synthesis approach using cetyltrimethyl–ammonium (CTA) as the sole organic template. The reduced crystal domain size and the presence of mesopores result in improved catalytic performance in methanol-to-hydrocarbon (MTH) reaction as compared to bulk ZSM-5. We investigated the role of the base (LiOH, NaOH, KOH, RbOH, CsOH), the H2O/CTA ratio, the Si/Al ratio and counter-ion of CTA (OH−vs. Br−). The crucial role of KOH and RbOH is evident as only these bases allow dissolution of the amorphous silica–alumina precursor to such extent that zeolite crystallization occurs. With other bases, silica dissolution is too limited to start zeolite crystallization, corroborated by the observation that seeding the synthesis gel rapidly led to mesoporous ZSM-5 zeolite for all bases. With KOH, mesoporous zeolite was obtained in the H2O/CTAOH 800–3200 range. The role of Al is also important as without it only ZSM-48 zeolite could be formed, while a too high Si/Al ratio of 20 did not lead to nucleation. A highly crystalline, hierarchical ZSM-5 free from extraframework Al synthesized from a gel with KOH as base, H2O/CTAOH and Si/Al ratios of 800 and 50, respectively displayed the highest catalytic performance in the MTH reaction, outperforming bulk ZSM-5.