Nanosized LiNi1/3Co1/3Al1/3O2 with an α-NaFeO2 structure has been successfully synthesized via a water-in-oil microemulsion method. Well-crystallized LiNi1/3Co1/3Al1/3O2 was obtained after heating at 800°C for merely 3h. The particle size of the microemulsion-derived powders was around 30nm. The results of electrochemical analysis revealed that the synthesized powders exhibited higher discharge capacity at elevated temperatures than at room temperature. The Co3+/Co4+ redox reactions are considered to play an important role in the discharge capacity and capacity retention of synthesized LiNi1/3Co1/3Al1/3O2.