A multi-stable electroresponsive smart window and preparation method thereof are disclosed. The multi-stable electroresponsive smart window comprises a first light transmitting conductive substrate, a parallel orientation layer, a positive polymer stabilized cholesteric texture layer, a positive cholesteric texture layer and a second light transmitting conductive substrate disposed in stack successively. The multi-stable electroresponsive smart window of the present disclosure can realize a diversified light transmission state such as colored and transparent state, colored and blur state, colorless and blur state, and colorless and transparent state by changing the magnitude of the access voltage, thereby satisfying the various demands in people's work and life. In addition, the multi-stable electroresponsive smart window of the present disclosure has the characteristics of simple production, rich patterns, energy saving and environmental protection, which has good application prospects in the fields of window glass, home glass window and glass curtain wall, and the like.