Belonging to the field of electronic composite materials and nano-functional materials, the invention provides a double-layer structure flexible piezoelectric film with high output, a preparation andapplication method thereof. A layer-by-layer solution spin coating-heat treatment process is adopted, an inorganic piezoelectric material is used as the filler to enhance the piezoelectric output of the composite film, and the double-layer structure is utilized to acquire high output and good mechanical properties at the same time. The inorganic filler is nanoparticles or nanofiber of barium titanate, barium strontium titanate, lead zirconate titanate and other piezoelectric ceramics, or nanoparticles or nanofiber of magnesium oxide, zinc oxide and other metal oxides, or multiwalled carbon nanotube. The polymer matrix can be polyvinylidene fluoride, polyvinylidene fluoride-trifluoroethylene, polyvinylidene fluoride-trifluoroethylene-hexafluoropropylene and other materials. By adjusting thefiller content and the filler distribution in the double layers, the filler efficiency can be improved. The composite material has the characteristics of good flexibility, high piezoelectric output,high sensitivity and light weight, and can be used as a power supply of wearable equipment, as a flexible sensor to detect human activities and the like.