A series of LiM1xM2yMn2−x−yO3.8F0.2 (M1 = Cr, M2 = V; x = y = 0.2) cathodes, viz., LiMn2O3.8F0.2, LiCr0.2Mn1.8O3.8F0.2 and LiCr0.2V0.2Mn1.6O3.8F0.2 along with native LiMn2O4 have been synthesized by Citric Acid assisted Modified (CAM) sol–gel method, with a view to understand the effect of synthesis methodology and the effect of dual category dopants, viz., anion and/or cation upon spinel cathodes individually. An acceptable capacity retention (94%) observed up to 50 cycles for native LiMn2O4 cathodes is attributed to the significance of CAM sol–gel method. Similarly, the encouraging charge–discharge results of LiMn2O3.8F0.2 (130 mAh g−1) and LiCr0.2Mn1.8O3.8F0.2 (142 mAh g−1) cathodes revealed a possible augmentation in the reversible capacity behavior of the spinels upon F− substitution at 32e site and the simultaneous substitution of Cr3+ and F− at 16d and 32e sites respectively.