Ni(OH)₂ and H₄SiO₄ are the two key intermediates for the synthesis of Ni-phyllosilicate, and the purpose of this work is to reveal which one is more efficient. The silica (D) was extracted from distillers’ grains, which was used as the sacrificial template for Ni-phyllosilicate. The formation of Ni(OH)₂ and H₄SiO₄ was enhanced by NaOH and NH₄F, respectively, and Ni/D-S (assisted by sodium hydroxide) and Ni/D-A (assisted by ammonium fluoride) were obtained. Although the amount of NaOH and NH₄F and hydrothermal synthesis procedures were identical, there was a significant difference of their Ni contents. The Ni content of Ni/D-S and Ni/D-A was 17.7 wt% and 2.5 wt%, respectively. As a result, Ni/D-S was more active for CO₂ methanation, whose CH₄ yield reached 61.6% at 450 °C, 0.1 MPa, 60 L g⁻¹·h⁻¹, while the maximum CH₄ yield of Ni/D-A was only 16.4% at 500 °C. However, the formation of Ni-phyllosilicate could also be improved after addition of more NH₄F, and the increased amount of H₄SiO₄ led to the high Ni content (33.4 wt%) of Ni/D-A-M (M refers to the addition of more ammonium fluoride) and enhanced catalytic performance for CO₂ methanation. It was concluded that Ni(OH)₂ and H₄SiO₄ were both important for the synthesis of Ni-phyllosilicate, while Ni(OH)₂ was the more efficient one.