Polylactic acid has good biodegradability and processability, but its flammability and serious droplet characteristics limit its development and application. Therefore, developing safer flame‐retardant PLA materials is crucial. This research develops a novel flame‐retardant polylactic acid (PLA) material blend, utilizing aluminum diethylphosphinate (AlPi), piperazine pyrophosphate (PAPP), and β‐cyclodextrin. Optimal synergy occurs at a 5:1 PAPP/β‐CD mass ratio with 4 wt.% AlPi. This combination significantly reduces the heat release peak from 294.89 to 144.21 kW·m−2 and generates non‐combustible residues. The sample forms a stable, uniform carbon layer during combustion due to hydrogen bond crosslinking and Lewis acid–base reactions. The activation energy (Eα) is raised from 264.99 to 281.08 kJ·mol−1 between 312 and 402°C. Thus, an AlPi‐PAPP‐β‐CD based P‐C‐N composite flame retardant is investigated, offering a promising research direction for developing fire‐safe polylactic acid materials. This research may yield valuable insights for diverse applications.