Biodegradable polylactide (PLA) has been widely utilized in people’s daily lives. In order to improve the fire safety of PLA, ammonium polyphosphate (APP) was self-assembled onto the surface of serpentine Ni3Si2O5(OH)4 through the electrostatic method, followed by mixing with PLA by melt compounding. The APP-modified serpentine (serpentine@APP) dispersed uniformly in the PLA matrix. Compared with pure PLA, the PLA composite with 2 wt% serpentine@APP reduced the peak heat release rate (pHRR) and total heat release (THR) by 43.9% and 16.3%, respectively. The combination of APP and serpentine exhibited suitable synergistic flame-retardant effects on the fire safety enhancement of PLA. In addition, the dynamical rheological tests revealed that the presence of APP and serpentine could reduce the viscosity of PLA composites. The plasticizing effects of APP and serpentine benefited the processing of PLA. The mechanical properties of PLA/serpentine@APP maintained suitable performance as pure PLA. This study provided a feasible way to enhance the fire safety of PLA without sacrificing its mechanical properties.