The invention provides a preparation method of catalyst applied to tert-butylamine production through direct amination of isobutene and an application. The catalyst is an overall F-ZSM-11 binder-free molecular sieve. The preparation method of the catalyst comprises steps as follows: performing hydrothermal treatment on a mixture formed by an ammonium fluoride and silica binder and an HZSM-11 molecular sieve raw powder in a tetrabutyl ammonium hydroxide aqueous solution or steam to form the overall F-ZSM-11 binder-free molecular sieve; performing further drying and roasting to prepare the needed catalyst. In a tert-butylamine production process through direct amination of isobutene, the catalyst has the characteristics of high reactivity, low reaction pressure and temperature and high target product selectivity.