Bio-based, cost-effective carbon nanofibers are fabricated from polyacrylonitrile (PAN) – refined biotechnology humic acids (RB) via simple eletrospinning after stabilization and carbonization. The influence of PAN/RB mass ratios and heat-treatment temperatures (HTTs) on structure and morphology is systematically studied. Excitingly, a first discharge/charge capacity of 937.9/613.4mAhg−1(coulombic efficiency of 65.4%) is achieved at 20mAg−1 for PB7/3-800 in lithium-ion batteries (LIBs). Meanwhile, a charge capacity of 348.2mAhg−1 (about 89% retention ratio) remains even after 100 cycles at 0.1Ag−1. It is demonstrated that biomass humic acids can be applied as a promising precursor to fabricate high performance, low-cost, as well as “green” carbon electrode material for LIBs.