The invention provides a catalyst for preparation of 2,3,5-trimethylhydroquinone by hydrogenation of 2,3,5-trimethylbenzoquinone and a preparation method of the catalyst. A precursor of the catalyst is composed of carboxylic acid functionalized polystyrene (PS) nanospheres and a zeolite imidazole framework (ZIF) composite structure with a shell layer containing Zn/Ni mixed metals, the precursor ofthe catalyst is subjected to pyrolysis in the N2 atmosphere at 800-1100 DEG C to remove the PS nanospheres to form a hollow structure, at the same time, metal Zn in the ZIF is removed to form a N-doped porous carbon structure, subsequent acid treatment is performed, and finally the N-doped porous carbon supported metal Ni catalyst having a hollow structure is obtained, wherein metal Ni accounts for 2%-10% of a total weight of the catalyst, and heteroatom N accounts for 2%-8% of the total weight of the catalyst. The catalyst provided by the invention has high catalytic performance when used for preparation of the 2,3,5-trimethylhydroquinone by hydrogenation of the 2,3,5-trimethylbenzoquinone.