Flame-retardant silicate-intercalated calcium aluminum hydrotalcites (CaAl-SiO3-LDHs) were synthesized to treat bamboo for retardancy, to overcome the bamboo’s flammability and reduce the production of toxic smoke during combustion. The microstructure, elemental composition, flame retardancy, and smoke suppression characteristics of the bamboo before and after the fire-retardant treatment with different pressure impregnation were studied using a scanning electron microscope (SEM), elemental analysis (EDX), and cone calorimetry. It was found that CaAl-SiO3-LDHs flame retardants can effectively fill and cover the cell wall surface and the cell cavity of bamboo without damaging the microstructure. As compared to the non-flame-retardant bamboo, the heat release rate (HRR) of the CaAl-SiO3-LDHs flame-retardant bamboo was significantly reduced, the total heat release (THR) decreased by 31.3%, the residue mass increased by 51.4%, the time to ignition (TTI) delay rate reached 77.8%, the mass loss rate (MLR) decreased, and the carbon formation improved. Additionally, as compared to the non-flame-retardant bamboo, the total smoke release (TSR) of the CaAl-SiO3-LDHs flame-retardant bamboo decreased by 38.9%, and the carbon monoxide yield (YCO) approached zero. Thus, the CaAl-SiO3-LDHs flame-retardant bamboo has excellent flame-retardancy and smoke suppression characteristics.