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Developing flame-retarded polybutylene succinate (PBS) is a challenging task owing to its high flammability, noncharring, and melt-dripping during burning. In this work, based on the synergistic combination between piperazine pyrophosphate (PAPP) and zinc borate (ZnB), a promising intumescent PBS system was developed as an efficient strategy to impart PBS with improved flame retardancy and antidripping properties. The results showed that PBS/PAPP15%/ZnB5% passed V-0 rating in the UL-94 vertical burning test (3 mm), while only a V-2 rating was achieved for PBS/PAPP20%. Compared to PBS/PAPP20%, the combination of PAPP and zinc borate (ratio of 15:5) led to significant reductions in the peak heat release rate (pHRR, −55%), fire growth rate index (FIGRA, −40%), and maximum average rate of heat emission (MARHE, −47%) evaluated by mass loss cone calorimetry. Meanwhile, the flame retardancy index of PBS/PAPP15%/ZnB5% reached up to 5.18 and the flameout time significantly increased to 1049 s. Fourier transform infrared and solid-state nuclear magnetic resonance analyses were employed to gain insight into the reaction-to-fire mechanism in the condensed phase. The results confirmed the fact that the formation of a crackfree protective intumescent char layer, reinforced by thermally stable inorganic species (boron−zinc phosphates), effectively restricted the heat and fuel transfer between condensed and gas phases, hence resulting in the excellent enhancement in flame retardancy.