The purpose of this paper lies in the preparation and utilization of phenolic resin hollow microspheres to enhance the induced carbonization performance of polymer materials and endow higher fire safety. PHM (phenolic resin hollow microspheres), CPHM (carbonized phenolic resin hollow microspheres), and CAPHM (carbonized phosphorylated phenolic resin hollow microspheres) were used as fillers in thermoplastic polyurethane elastomer. With the incorporation of 4 wt.% CPHM, as compared to pure TPU, the peak heat release rate (pHRR), total smoke release (TSR), and the peak CO release rates are decreased by 64.4%, 37.9%, and 86.2%, respectively. Simultaneous enhancement in flame retardancy, smoke suppression, and toxicity reduction is attributed to the formation of a compact residual layer in the polymer matrix, which significantly retards the dispersion of combustible gas, smoke particles, and toxic gas from the underlying substrate. Such outstanding characteristics make carbon microspheres a promising candidate for high fire safety polymers. [ABSTRACT FROM AUTHOR]