Although the energy densities of batteries continue to increase, safety problems (for example, fires and explosions) associated with the use of highly flammable liquid organic electrolytes remain a big issue, significantly hindering further practical applications of the next generation of high-energy batteries. We have fabricated a novel "smart" nonwoven electrospun separator with thermal-triggered flame-retardant properties for lithium-ion batteries. The encapsulation of a flame retardant inside a protective polymer shell has prevented direct dissolution of the retardant agent into the electrolyte, which would otherwise have negative effects on battery performance. During thermal runaway of the lithium-ion battery, the protective polymer shell would melt, triggered by the increased temperature, and the flame retardant would be released, thus effectively suppressing the combustion of the highly flammable electrolytes.