In the present work, a core-shell structured Co/SiO2@HZSM-5 catalyst was prepared for hydrogen production from syngas of plastic waste gasification. The cobalt catalyst was coated with HZSM-5 shell through a hydrothermal process, and the Co/SiO2@HZSM-5, with different loadings of HZSM-5 (e.g., 10–30 wt %) exhibited excellent activity and durability for dehydrogenation reactions. The amount of HZSM-5 was found to be an important factor for hydrogen production. Temperature-programmed reduction with H2 and temperature-programmed desorption of ammonia was applied to determine the active site and the acidity of prepared catalyst, respectively. The prepared Co/SiO2@HZSM-5 was tested through reforming of plastic gasification syngas and shown superior hydrogen production ability (∼90%) and stability (over 15 h). The effects of reduction-oxidation behavior on the catalytic performance were also discussed. •The core-shell catalyst showed superior performance than traditional catalysts.•Mesoporous HZSM-5 shell prevented the active phase core from deactivation.•Co/SiO2@HZSM-5 catalyst was synthesized for hydrogen promotion.