79Se is a fission product in spent fuel with a half-life of up to 6.5 × 104 a, which is not controlled by solubility in aqueous solution and has strong mobility. These characteristics make it highly susceptible to migration in groundwater. Meanwhile, due to the negative charge of selenium ions, they are difficult to be fixed by buffer/backfill materials, engineering materials, geological materials and commonly used adsorption methods in near-field geochemical environments. Therefore, the fixation of 79Se has become a hot and difficult research topic both domestically and internationally. Therefore, this article aimed to simulate the removal of radioactive nuclide Se(IV) from high-level radioactive waste disposal repositories. On the basis of siderite (FeCO3), by adding zero-valent nickel (Ni0) and continuously optimizing sample preparation conditions, an economical, efficient and stable siderite/zero-valent nickel (FeCO3/Ni0) composite material was successfully prepared. Experimental studies on the removal of Se(IV) from solution were conducted under different conditions and the material was characterized using various modern methods from macro and micro perspectives, the performance and mechanism of FeCO3/Ni0 composite material for removing Se(IV) was explored deeply. The research results indicated that FeCO3/Ni0 had high potential as a candidate adsorbent for the removal of Se(IV) due to its easy synthesis, low-cost, high adsorption capacity and strong reduction.