The Polyvinylpyrrolidone (PVP)-assisted polyol process was employed for the synthesis of lithium manganese phosphate (LiMnPO4) microflowers as a cathode material for Li-ion battery applications. LiMnPO4 microflowers were characterized by X-ray diffraction, scanning electron microscope, transmission electron microscope-energy dispersion spectroscope, and impedance spectroscopy. The microflowers were highly porous with nanosized petals. CR2032 coin cells were fabricated using LiMnPO4 microflowers’ sample and their battery characteristics were tested. The discharge capacity of LiMnPO4 microflowers was found to be 164 mAh g−1 at 0.1C. The observed high discharge capacity was attributed to the short diffusion length of Li-ion motion in the nanopetals of the LiMnPO4 microflowers.