Bamboo scrimber is widely used in interior decoration, architecture, and many other fields. However, it has caused huge security risks due to its inherent flammability and easy-to-produce toxic volatiles after combustion. In this work, the bamboo scrimber with superior flame retardant and smoke suppression properties was produced via the coupling of phosphocalcium-aluminum hydrotalcite (PCaAl-LDHs) with bamboo bundles. The results demonstrated that the flame-retardant bamboo scrimber (FRBS) heat release rate (HRR) and total heat release (THR) were, respectively, reduced by 34.46% and 15.86% compared with that of untreated bamboo scrimber. At the same time, the unique multi-layer structure of PCaAl-LDHs effectively slowed down the release rate of flue gas by extending its escape path. Cone calorimetry showed that the total smoke emissions (TSR) and specific extinction area (SEA) of FRBS were, respectively, reduced by 65.97% and 85.96% when the concentration of the flame retardant was 2%, which greatly developed the fire safety of the bamboo scrimber. This method not only improves the fire safety of bamboo scrimber but can also be expected to broaden its use scenarios.