The flammability and melt dripping of the widely used bio-based polyamide 11 (PA 11) have attracted much attention in the last decade, and they are still a big challenge for the fire science society. In this work, a novel single macromolecular intumescent flame retardant (AM-APP) that contains an acid source and a gas source was prepared by supramolecular reactions between melamine and p-aminobenzene sulfonic acid, followed by an ionic exchange with ammonium polyphosphate. The chemical structure of AM-APP was characterized by Fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy, and scanning electron microscopy. AM-APP and TiO2 were then introduced into PA 11 by melt compounding to improve the fire resistance of the composite. The fire performance of PA 11 composites was evaluated by the limiting oxygen index (LOI), vertical burning (UL-94), and cone calorimetry tests. The results showed that the presence of 22% AM-APP and 3% TiO2 increased the LOI value from 22.2 to 29.2%, upgraded the UL-94 rating from no rating to V-0, completely eliminated melt dripping, and significantly decreased the peak heat release rate from 943.4 to 177.5 kW/m2. The thermal behaviors were investigated by thermogravimetric (TG) analysis and TG-FTIR. It is suggested that AM-APP produces an intumescent char structure and releases inert gases, whereas TiO2 may consolidate the char layers, leading to the improvement in the fire resistance of PA 11.