A novel technology was developed to prepare microencapsulated red phosphorus (RP) with a coating of melamine cyanurate (MCA) serving as both a nitrogen-containing flame retardant and as a solid lubrication agent. We took advantage of the self-thickening effects during the MCA self-assembly process to realize effective encapsulation on the surface of predispersed RP powder. The technology described in this article can overcome several drawbacks of current microencapsulation processes including (1) relatively complicated preparation processes, (2) use of formaldehyde or other noxious modifiers, and (3) poor compatibility with flame retardant fillers and polymer matrix resulting in poor physical properties. Additionally, this novel technology can also modify various properties of RP with regard to lubrication performance, ignition point, moisture absorption ratio, and color. As a composite system of flame retardant phosphorus encapsulated by a nitrogen-containing flame retardant, the microencapsulated RP showed nitrogen-phosphorus (N-P) synergism with further improved flame retardancy. The action and mechanisms of the microencapsulated RIP flame retardant polyamide 6 (PA6) were investigated by limiting oxygen index, vertical burning experiment (UL94), thermogravimetric analysis, and scanning electron microscope observations. The results indicated that the flame retardant PA6 possessed desired flame retardancy because of effective char-formation of the condensed phase and it also showed satisfactory mechanical properties as the result of the good compatibility between flame retardant and PA6 resin.