There is controversy in the literature regarding the existence of the metastable γ′ phase with an ordered Ll2 structure in rapidly solidified Fe–Ni–Al–C alloys. In this study, the quench rate–metastable structure dependence was examined in the Fe–20Ni–8Al–2C (weight percent) alloy. The effect of silicon on the kinetics of phase formation was studied by adding two weight percent silicon to a base alloy of Fe–20Ni–8Al–2C. Samples were rapidly solidified in an arc hammer apparatus and examined by transmission electron microscopy. In the Fe–20Ni–8Al–2C alloy, the nonequilibrium γ′ and γ phases were found in foils 65 to 100 μm thick. At higher quench rates, i.e., thinner samples, the matrix was observed to be disordered fcc γ with K-carbide precipitates. Samples containing silicon were found to have a matrix composed of γ′ and γ structures when the foils were thicker than 40 μm. At higher quench rates, the matrix was disordered fcc γ with K-carbide precipitates. The nonequilibrium γ′ and γ structures are present in samples with or without silicon, but are observed at higher cooling rates with the addition of silicon. This sensitivity to cooling rate and composition in resulting metastable structures may explain the differences reported in the literature for these rapidly solidified materials.