High-efficiency adsorbents are essential for ultradeep desulfurization through selective adsorption, which features low energy consumption without causing secondary pollution. Aluminum oxide is always added as a binder to form physically bound pellets, which weakens the adsorptive desulfurization performance. In this work, a novel micro-mesoporous binderless ZSM-5 (BL-ZSM-5) was successfully prepared through in situ crystallization, which could efficiently remove thiophene from model fuel. Desulfurization ability was investigated by static and fixed bed adsorption. The breakthrough adsorption capacity of thiophene on BL-ZSM-5 reaches 0.38 mg/g, which is twice as high as that of ZSM-5 with alumina binders (AI-ZSM-5). The improvement is attributed to the conversion of alumina into molecular sieves, which could increase the adsorption sites and provide appropriate mesoporous channels for thiophene transfer. The thermal stability of BL-ZSM-5 is superior to that of AI-ZSM-5. The adsorption performance of BL-ZSM-S is maintained well after 6 cycles of regeneration. The results demonstrate that the attractive prospect of BL-ZSM-5 in highly efficient desulfurization of transport fuels through selective adsorption.