With the development of portable electronic devices, it is an urgent demand to miniaturize energy storage components, especially for Li-ion batteries, and the thin-film electrode is a promising miniaturization strategy. In this work, we successfully fabricated a binder-free thin-film electrode of LiFePO4/C by a spray drying method. According to the scanning electron microscopy, the Al-foil substrate was coated with a porous LiFePO4/C layer of ca. 4 µm thick, and the X-ray diffraction and the Raman spectra reveal the good crystallization of LiFePO4 and the presence of amorphous carbon. The as-prepared electrode exhibits an excellent cycle stability, which works quite good even after 2000 cycles. Thereby, we suggested that the as-prepared binder-free thin-film electrode can be potentially applied in the field of all-solid-state, flexible, and micro Li-ion batteries.