In this study, we explored the rational integration of layered double hydroxides (LDHs) with reduced graphene oxide (rGO) to create a hierarchical nano/microarray structured CuMgAl-LDH/rGO hybrid aimed at enhancing the flame retardancy and smoke suppression properties of polymer nanocomposites. The results indicated that the limiting oxygen index (LOI) value of the G-CuMgAl/polyvinyl chloride (PVC) composite reached 35.8%, reflecting a 6.4% increase compared to pristine PVC (29.4%), and achieved a UL-94 V-0 rating. Furthermore, in comparison to pristine PVC, the peak heat release rate (PHRR) of the G-CuMgAl/PVC composite was significantly reduced by 40.2%; the total heat release rate (THR) decreased by 24.3%; the maximum average heat release rate (MARHE) diminished by 41.6%; the peak smoke production (PSPR) decreased by 37.8%; the total smoke production (TSP) was reduced by 31.3%; and the average effective heat of combustion (av-EHC) decreased by 15.2%. The enhanced flame retardancy and reduced smoke production can primarily be attributed to the multiple synergistic interactions among the highly dispersed constituents and the nano/microstructures, which effectively impede the transfer of heat, mass, and O2 from various directions while preventing further combustion of the underlying matrix by creating a tortuous path in the condensed phase. Additionally, this study provides a novel perspective on the design and synthesis of structured LDHs/rGO hybrids, with the potential to enhance flame retardancy and smoke suppression properties across a broad spectrum of polymer materials.