Heteroatom-doping has been regarded as an effective strategy to regulate the Na storage performance of carbon materials. In this paper, N and O dual-doped carbon microspheres (NO-CS) from the rinds of corn stalks have been fabricated via a tailored carbonization and solution doping route. NO-CS reveals both high O (15.6 at.%), N (6.4 at.%) contents and high specific surface area (746.48 m2 g−1). The NO-CS derived carbon anode shows tremendous reversible capacity, rate capability and cycling stability, e.g. 270 mAh g−1 over 200 cycles at 50 mA g−1, 130 mAh g−1 over 3500 cycles at 5 A g−1. The superior Na storage property may due to the abundant porosity and dual-doping that boost fast ion adsorption at the graphene layer defects and nitrogen oxygen moiety of carbon. Scalable and cost-effective synthesis route with outstanding Na storage performance makes NO-CS a competitive anode material for Na-ion batteries.