Owing to the preponderances in easy preparation and low cost, N-doped foam flame retardant polystyrene (FRPS) could be regarded as a sustainable precursor to develop porous carbonaceous frameworks for the encapsulation of elemental selenium. In this paper, an electrode material of Se encapsulated in N-doped foam flame retardant polystyrene based porous carbon framework (Se@KF65) was fabricated by carbonization/activation of N-doped foam polystyrene and selenium-loading for high-performance lithium batteries. Due to the fact that KF65 acted as a stable matrix for Se and facilitates electronic conductivity and ion transportation, the Se@KF65 composite exhibited large reversible capacity, high rate performance and durable long-term cycling stability. Moreover, the high specific surface area, large pore volume and good electron conductivity of Se@KF65 composite showed the reversible electrochemical reaction of selenium towards metallic Li,and at the current density of 1 A g(-1), Se@KF65 composite electrode exhibited a reversible capacity of 917.8 mAh g(-1) after 600 cycles. The easily obtained mi/macrospores features of Se@KF65 composite indicated that large-scale treatment of the polymer material may find its potential application in renewable green energy storage.