An　eco-friendly　strategy　for　the　synthesis　of　highly　ordered　meso-　and　microporous　zeolites　is　required　both　in　academia　and　industry.　Therefore,　asymmetrical　anionic-nonionic　gemini　surfactants,　polyoxyethylene　laurinol　ether　sodium　sulfoitaconate　(Gemini-n),　have　been　designed,　synthesized　and　used　in　the　directed　synthesis　of　hierarchical　ZSM-5　zeolites　(HZSM-5)　by　imparting　substantial　mesoporosity.　The　hydrothermal　temperature,　the　amount　of　gemini　surfactants　and　the　crystallization　time　strongly　affected　the　crystallization　degree　and　the　textural　properties　of　the　HZSM-5.　The　tune　of　the　porous　size　distribution　(microporous　to　mesoporous)　can　be　obtained　by　varying　the　number　of　the　ethylene　oxide　units　in　the　gemini　surfactants.　Besides,　the　use　of　these　novel　anionic-nonionic　gemini　surfactants　is　an　effective　strategy　to　avoid　phase-separation.　The　existence　of　abundant　hydroxyl　groups　on　the　surface　of　HZSM-5　was　used　to　immobilize　molybdenum　compound　by　the　stable　Mo−O　bond.　The　complex　with　abundant　intercrystal　mesopores　exhibited　superior　catalytic　performance　with　high　yield　and　selectivity　for　the　epoxidation　reactions　of　alkenes　as　compared　to　the　conventional　ZSM-5.　Moreover,　the　complex　presented　high　catalytic　ability　after　been　reused　for　five　times.　©　2021　Wiley-VCH　GmbH