The invention relates to a preparation method for copper-zinc-tin-sulfur photoelectric fibers, and belongs to the technical field of a photovoltaic material. The preparation method comprises the steps of performing preprocessing on waste copper slag, then carrying out calcining, grinding, magnetic separating and ball milling to obtain a ball-milled mixed powder; then mixing the mixed power with citric acid and glacial acetic acid, and then performing heating, stirring and mixing on the mixture, and polyvinyl alcohol and ethanol amine to obtain a precursor solution; and finally, carrying out electrostatic spinning on the precursor solution to obtain the copper-zinc-tin-sulfur photoelectric fibers. The copper-zinc-tin-sulfur photoelectric fibers prepared by the method are high in sunlight utilization rate; the photoelectric efficiency can reach 8.5-8.8%; and the carrier mobility is higher than 30.25cm<2>v<-1>s<-1>.