The main aim of this research is the examination of the physicochemical properties and their impact on the electrochemical activity of carbon materials obtained from the starch of different botanical origin (SCs). The obtained materials are compared to graphene nanoplatelets (GNPs) of different particle sizes (5 and 25 µm) applied as an anode active material for high-performance lithium-ion cells. SCs were obtained via thermal carbonization and this process enables an obtainment of better sorption properties compared to GNPs. The excellent electrochemical properties are mainly attributed to the good DLi+ (3.03 × 10−13–7.64 × 10−11 cm2 s−1 for SCs and 7.60 × 10−13–5.42 × 10−12 cm2 s−1 for GNPs) and relatively small resistances (EIS). However, the primary focus is on the specific capacity and cyclability. The capacity retentions of CSC cycled at 1 mA g−1, 10 mA g−1, 50 mA g−1, 1 mA g−1 for 50 cycles are 98%, 99%, 96%, 94% with specific capacities equal to 820, 800, 790, 1000 mAh g−1, respectively. The 5GNPs and 25GNPs may present a much smaller reversible capacity of 650, 600 mAh g−1 at 10 mA g−1. The thermal modification process of starches is simple, safe and widely applied, providing new paths for rational engineering of anode materials for LIBs. Moreover, the applied materials are easily available worldwide and are promising in the well-known Green Chemistry aspect making the cells more biodegradable.Graphic