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Epoxy resin (EP) has been favored in extensive fields. Nevertheless, the notorious issue of high fire hazard has been a nonnegligible bottleneck for its extended application. Here, a Jadeite original stone inspired PBA core-shell architecture (Co–Fe–Co PBA) is constructed towards fire retardation and toxicity elimination of EP. This architecture holds high strengths in physically blocking and chemically catalyzing towards released volatiles, leading to markedly impaired fire hazard. By using 2.0 wt% Co–Fe–Co PBA, the peak heat release rate and total heat release values are decreased by 40.2% and 33.8% whilst the peak smoke production rate and total smoke production are reduced by 43.7% and 35.2%. Also, the inhibited emissions of toxic gases including CO, NO and HCN, are discovered. Of note, the promotion in impact strength can be acquired. In brief, this work may be encouraging for the construction of PBA based hierarchical architecture, as cornerstones for fire-safe polymer composites with low toxicity.