Gluconate is known to mediate metal leaching. However, during bioleaching by e.g., Gluconobacter oxydans, gluconate can be oxidized to 2-ketogluconate and 5-ketogluconate. The impact of bio-oxidation of gluconate on metal leaching has not been investigated. Therefore, the aim of this study was to investigate leaching of rare earth elements (REEs) and base metals from spent nickel-metal-hydride (NiMH) batteries using gluconate, 2-ketogluconate and 5-ketogluconate. Batch leaching assays were conducted under controlled and uncontrolled pH conditions for 14 days using 60 mM of either the individual leaching agents or their various combinations. At target pH of 6.0 ± 0.1 and 9.0 ± 0.1 and without pH control, complexolysis was the dominating leaching mechanism and higher REE leaching efficiency was obtained with gluconate, while 5-ketogluconate enabled more efficient base metal leaching. At target pH of 3.0 ± 0.1, acidolysis dominated, and the base metal and REE leaching yields with all the tested leaching agents were higher than under the other studied pH conditions. The highest base metal and REE leaching yields (%) were obtained using gluconate at target pH of 3.0 ± 0.1 being 100.0 Mn, 90.3 Fe, 89.5 Co, 58.5 Ni, 24.0 Cu, 29.3 Zn and 56.1 total REEs. The obtained results are useful in optimization of heterotrophic bioleaching.