The synergistic flame retardancy of aluminium dipropylphosphinate (ADPP) and melamine (ME) in polyamide 6 (PA6) was studied by the limiting oxygen index (LOI) measurement, the vertical burning test, and the cone calorimeter test, and the mechanism was also discussed by thermogravimetric and residual analyses. The experimental results indicated that there was obvious synergistic flame retardancy between ADPP and ME under their appropriate weight ratios. The thermogravimetric results and the analysis of the residues obtained in cone calorimeter test showed that ADPP and ADPP/ME played the role of flame retardance by gaseous- and condensed-phase mechanisms, where, on one hand, they were decomposed into nonvolatile aluminum phosphate and promoted the carbonization of PA6, and the formed intumescent layer resulted in flame retardancy by the barrier effect on heat, air, and decomposition products, and on the other hand, they were decomposed into volatile phosphorus compounds which bring about flame retardancy by flame inhibition. Using a combination of ADPP and ME improved charring of PA6 and raised the residual rate of P and Al, thus, improving the barrier effect in the condensed phase.