Fluorapatite protective films were prepared on marble substrates using a biomimetic method. By mimicking the mineralization mechanism of enamel, phosphorus and fluorine were introduced on the surface of the marble substrate. In the presence of a biological template, namely collagen, an integrated fluorapatite film was produced and the marble substrate was entirely covered. The prepared fluorapatite films were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), and energy dispersive X-ray (EDX) spectroscopy. The performances of the fluorapatite films were evaluated by color changes, capillary water absorption, and acid resistance tests. The results revealed that the fluorapatite films had good compatibility with the marble substrate; the physical properties such as color and capillary water adsorption of the marble substrates were unchanged. The fluorapatite films also had good acid resistance and were stable even in heavy acid rain. Fluorapatite protective films were prepared on marble substrates using a biomimetic method. By mimicking the mineralization mechanism of enamel, phosphorus and fluorine were introduced on the surface of the marble substrate. In the presence of a biological template, such collagen, an integrated fluorapatite film was produced and the marble substrate was entirely covered. The prepared fluorapatite films were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), and energy dispersive X-ray by color changes, capillary water absorption, and acid resistance tests. The results revealed that the fluorapatite films had good compatibility with the marble substrate; the physical properties such as color and capillary water adsorption of the marble substrates were unchanged. The fluorapatite films also had good acid resistance and were stable even in heavy acid rain.