Spinel LiMn2O4 particles were successfully synthesized by an ultrasonic spray pyrolysis method from the precursor solutions; various combinations of nitrate, acetates or formats of lithium and manganese were stoichiometrically dissolved in distilled water. The product characteristics, such as crystallinity, specific surface area, particle morphology and interior structure of particles, were examined with X-ray diffraction (XRD), the Brunauer–Emmet–Teller (BET) method, field emission scanning electron microscopy (FE-SEM) and transmission electron microscopy (TEM). All the samples exhibited a pure cubic spinel structure without any impurities in the XRD patterns, while the surface morphology of as-prepared powders was classified into four patterns and the interior structure three patterns. The as-prepared samples were then used as cathode active materials for lithium-ion battery, and electrochemical studies were carried out on the charge/discharge characteristics of the Li/LiMn2O4 cells. The effect of LiMn2O4 particle properties such as crystallite size, specific surface area and particle morphology on the electrochemical properties were also discussed in details.