Development of facile and cost-effective routes to achieve hierarchical porous and heteroatoms-doped carbon architectures is urgently needed for high-performance supercapacitor application. In our study, ternary-doped (nitrogen, phosphorus and oxygen) hollow carbon microspheres (NPO-HCSs) are fabricated by one-step pyrolysis of single poly(cyclotriphosphazene-co-phloroglucinol) (PCPP) microsphere, which is generated through a facile polymerization between hexachlorocyclotriphosphazene and phloroglucinol at mild conditions. The whole preparation process is not used any additional template or activating agent. The obtained NPO-HCS-950 with average diameter of 580 nm and shell thickness of about 80 nm have a high specific surface area (2390 m(2) g(-1)), a large pore volume (1.35 cm(3) g(-1)), hierarchically interconnected pore texture, and uniform ternary heteroatom doping (O: 3.04 at%; N: 1.33 at% and P: 0.67 at%). As an electrode material for supercapacitors, the specific capacitance of the NPO-HCS-950 reaches 253 F g(-1) of 1 A g(-1) and 176 F g(-1) at 20 A g(-1), revealing superior rate performance. The capacity retention after 10,000 consecutive charge-discharge cycles at 20 A g(-1) is up to 98.9%, demonstrating excellent cycling stability. Moreover, the assembled symmetric supercapacitor using NPO-HCS-950 exhibits a relatively high energy density of 17.6 W h kg(-1) at a power density of 800 W kg(-1). Thus, a promising electrode material for high-performance supercapacitors is obtained through a facile, green and scalable synthesis route. (C) 2018 Elsevier Inc. All rights reserved.