Maricite NaFePO4 (m-NaFePO4) was investigated as a positive electrode material for intermediate-temperature operation of sodium secondary batteries using ionic liquid electrolytes. Powdered m-NaFePO4 was prepared by a conventional solid-state method at 873 K and subsequently fabricated in two different conditions; one is ball-milled in acetone and the other is re-calcined at 873 K after the ball-milling. Electrochemical properties of the electrodes prepared with the as-synthesized m-NaFePO4, the ball-milled m-NaFePO4, and the re-calcined m-NaFePO4 were investigated in Na[FSA]-[C2C1im][FSA] (C2C1im+ = 1-ethyl-3-methylimidazolium, FSA− = bis(fluorosulfonyl)amide) ionic liquid electrolytes at 298 K and 363 K to assess the effects of temperature and particle size on their electrochemical properties. A reversible charge-discharge capacity of 107 mAh g−1 was achieved with a coulombic efficiency >98% from the 2nd cycle using the ball-milled m-NaFePO4 electrode at a C–rate of 0.1 C and 363 K. Electrochemical impedance spectroscopy using m-NaFePO4/m-NaFePO4 symmetric cells indicated that inactive m-NaFePO4 becomes an active material through ball-milling treatment and elevation of operating temperature. X-ray diffraction analysis of crystalline m-NaFePO4 confirmed the lattice contraction and expansion upon charging and discharging, respectively. These results indicate that the desodiation-sodiation process in m-NaFePO4 is reversible in the intermediate-temperature range.