Magnesium Phosphate Cement (MPC) exhibits high strength, exceptional high-temperature resistance, and outstanding adhesion properties at the steel interface, rendering it an ideal material for fire resistive coatings on steel structures. In this study, natural brucite powder was employed as the magnesium source, while hollow glass microspheres (HGM) were utilized as functional modifiers to formulate brucite-based MPC fire resistive coatings for steel structures. This research explored the influence of the mass ratio of brucite powder to ammonium dihydrogen phosphate (M/P), the brucite particle size, and the addition of HGM on the physical, mechanical, and fire-retardant properties of the coatings. The microstructure of the brucite-based MPC before and after fire testing was examined using SEM, XRD, TG-DTG, and X-CT. The results indicated that with an M/P ratio of 2.5:1 and a brucite particle size of 75–150 μm, the material exhibited optimal overall performance and was suitable as a matrix material for MPC. The incorporation of an appropriate amount of HGM increased the compressive strength of brucite-based MPC by 33.4 %, reduced the dry density by 20.5 %, extended the fire resistance of the structure, and decreased the thermal conductivity by 48.2 %. This can be attributed to: (i) HGM filling the pores in brucite-based MPC, creating a denser microstructure; (ii) HGM forming a closed porous structure with the MPC matrix, reducing thermal conductivity and increasing thermal resistance; (iii) The low thermal diffusivity of HGM/MPC impeded heat transfer, thereby decelerating thermal decomposition and flame propagation.