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One of the major drawbacks in Lithium-air batteries is the sluggish kinetics of the oxygen reduction reaction (ORR). In this context, better performances can be achieved by adopting a suitable electrocatalyst, such as MnO₂. Herein, we tried to design nano-MnO₂ tuning the final ORR electroactivity by tailoring the doping agent (Co or Fe) and its content (2% or 5% molar ratios). Staircase-linear sweep voltammetries (S-LSV) were performed to investigate the nanopowders electrocatalytic behavior in organic solvent (propylene carbonate, PC and 0.15 M LiNO₃ as electrolyte). Two percent Co-doped MnO₂ revealed to be the best-performing sample in terms of ORR onset shift (of ~130 mV with respect to bare glassy carbon electrode), due to its great lattice defectivity and presence of the highly electroactive γ polymorph (by X-ray diffraction analyses, XRPD and infrared spectroscopy, FTIR). 5% Co together with 2% Fe could also be promising, since they exhibited fewer diffusive limitations, mainly due to their peculiar pore distribution (by Brunauer–Emmett-Teller, BET) that disfavored the cathode clogging. Particularly, a too-high Fe content led to iron segregation (by energy dispersive X-ray spectroscopy, EDX, X-ray photoelectron spectroscopy, XPS and FTIR) provoking a decrease of the electroactive sites, with negative consequences for the ORR.