To realize the sustainability of Na-ion batteries (NIBs) for large-scale energy storage applications, a resource-abundant and cost-effective anode material is required. In this study, sugarcane bagasse (SB), one of the most abundant types of biowaste, is chosen as the carbon precursor to produce a hard carbon (HC) anode for NIBs. SB has a great balance of cellulose, hemicellulose, and lignin, which prevents full graphitization of the pyrolyzed carbon but ensures a sufficiently ordered carbon structure for Na+ transport. Compared with HC derived from waste apples, which are pectin-rich and have less cellulose than SB, SB-derived HC (SB-HC) has fewer defects and a lower oxygen content. SB-HC thus has a higher first-cycle sodiation/desodiation coulombic efficiency and better cycling stability. In addition, SB-HC has a unique flake-like morphology, which can shorten the Na+ diffusion length, and higher electronic conductivity (owing to more sp2-hybridized carbon), resulting in superior high-rate charge–discharge performance to apple-derived HC. The effects of pyrolysis temperature on the material characteristics and electrochemical properties, evaluated by using chronopotentiometry, cyclic voltammetry, and electrochemical impedance spectroscopy, are systematically investigated for both kinds of HC.