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Condensed-phase mechanisms play a major role in fire-retardant polymers. Generations of development have followed the concept of charring to improve fire properties. W1hereas the principal reactions are believed to be known, the specific description for multicomponent systems is lacking, as is the picture across different systems. A two-step approach is proposed in general, and also presented in greater detail. The second step covers the specific reactions controlling charring, whereas the actual reactants are provided in the preceding step. This model consistently incorporates the variety of structure-property relationships reported. A comprehensive case study is presented on seven phosphorus flame retardants in two epoxy resins to breathe life into the two-step approach.