The electrochemical performance of glucose-derived hard carbon (GDHC) anode has been evaluated using Li- and Na-salts in ethylene carbonate and propylene carbonate electrolyte mixtures. The LiPF6/EC:PC (1:1) system exhibits high capacity at low current densities (400 mAh g−1 at 25 mA g−1) and also good power characteristics retaining 150 mAh g−1 capacity at 2 A g−1 current density. The best overall performance was achieved with 1 M NaPF6/EC:PC (1:1) electrolyte based system with capacities of 175 mAh g−1 at 0.1 V vs Na/Na+ and 330 mAh g−1 at 1.5 V vs Na/Na+. The electrode has been physically characterized ex-situ using SEM, Raman and TOF-SIMS methods TOF-SIMS analysis revealed that the solid electrolyte interphase is more inorganic on the negative electrode in the Na-cell than on the negative electrode the Li-cell. The positive ion-specific images established by TOF-SIMS analysis show the non-homogeneous distribution of various fragments from the pristine GDHC, which is caused by slightly inhomogeneous mixture of GDHC and conducting carbon black (Super P®) particles.