The invention discloses a preparation method of a novel three-dimensional solar photo-thermal oil-water separator. The preparation method comprises the following steps: cutting foam Cu into a rectangle, and respectively cleaning the rectangular foam Cu with hydrochloric acid, absolute ethyl alcohol, acetone and deionized water for later use; preparing a mixed aqueous solution of sodium hydroxide and ammonium persulfate, soaking the cleaned the rectangular foam Cu in the mixed aqueous solution, taking out the rectangular foam Cu, cleaning the rectangular foam Cu with deionized water, soaking the rectangular foam Cu in sodium sulfide, taking out the rectangular foam Cu, bending the rectangular foam Cu into an inverted U shape, and enabling the inverted U-shaped Cu<x>S/foam Cu to vertically penetrate through a supportable substrate to obtain a Cu<x>S composite photo-thermal film with a three-dimensional hierarchical structure. The Cu<x>S composite photo-thermal film with the three-dimensional hierarchical structure prepared by the method adopts a composite copper-based sulfide material which is low in cost, high in light absorption capacity and high in photo-thermal conversion efficiency, so the manufacturing cost of a device is greatly reduced, and the stability of the device is improved; and photo-thermal efficiency is high, separation performance is good, any electric drive isnot needed, and cost performance is high.