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The aim of this paper was to investigate intumescent coatings based on polyfurfuryl alcohol (PFA) resin as a binder benefiting from high char yield and low smoke emission. To this end, the coatings composition in terms of PFA binder resin, long oil alkyd plasticizing resin, TiO2 pigment, and flame-retardant additives (FR) was changed as input parameters according to a mixture design-of-experiments. The corresponding changes in the backside temperature of mild steel substrate (Tb), residual char expansion ratio, limiting oxygen index, and char residue (wt% @1000 °C) were studied as the response variables describing fire performance characteristics of the coatings. The results showed that the backside temperature of the plate increased and the expansion ratio decreased with increasing in the alkyd resin concentration. Also, the flame-retardant efficiency of coatings strongly depends on the content of FR additives. When the content of PFA and alkyd resin was increased at a high level (35 and 4 wt%, respectively), the Tb of the coated plates reached 415 °C rapidly, due to the cracking of the coating and the lower concentration of FR additives. However, the formula with higher FR content, i.e., 68 wt%, showed the lowest Tb value ca. 128 °C. Flame-retardant characteristics directly depended on the expansion ratio of the coatings and the morphology of the char layer remaining on the substrate after the flame test; therefore, coatings with a higher expansion ratio showed lower backside temperature. The findings were supported by examining of the remaining char morphology after a flame test by optical microscopy and validated by comparing the predicted and actual responses for optimization. The value of absolute relative deviation was obtained in the range of 1.6–7.9, which indicates a good agreement between the proposed and experimental results. [ABSTRACT FROM AUTHOR]