To investigate the effect of matrix, counter ions and cycling conditions on the properties of mixed iron oxides, CaFe2O4, Li0.5Ca0.5(Fe1.5Sn0.5)O4 and NaFeSnO4 have been synthesized and their electrochemical performance studied. CaFe2O4 shows a reversible capacity of ∼200mAhg−1 at 60mAg−1 and 12–50cycles in the range 0.005–3.0V, but shows slight capacity fading when the upper voltage is reduced to 2.5V. Li0.5Ca0.5(Fe1.5Sn0.5)O4 gives a reversible capacity of ∼450mAhg−1 in the voltage range 0.005–3.0V at a current density of 60mAg−1 over 5–30cycles and shows slight capacity-fading up to 50cycles. NaFeSnO4 displays drastic capacity-fading on cycling to 3.0V, but has very good cycling performance (310–340mAhg−1 for to 4–110cycles) on cycling between 0.005 and 1.0V at 60mAg−1. The mechanism of operation of the electrodes, as well as the beneficial effects of the presence of Ca ions and cycling up to a 3.0V cut-off in the Ca-ferrites, are discussed.