The invention belongs to the technical field of intelligent materials and environmental materials, and particularly relates to a multiple response dendritic polythioether polymer prepared through a visible light initiated thiol-ene click reaction, and a preparation method thereof, wherein the intelligent multiple response dendritic polythioether polymer is successfully synthesized by using a sulfydryl compound and an acrylate compound as monomers through a thiol-ene click chemical reaction and a visible light initiated free radical polymerization method. According to the invention, the preparation method has the main advantages of environmental protection, simple operation, mild conditions and efficient reaction, does not use organic acids or alkali promoters to save the catalyst, and avoids the problem of residual metal catalyst; and the prepared and synthesized multiple response dendritic polythioether polymer shows excellent photosensitive behaviors, further has pH and redox dependence on the photosensitive behaviors, and is a novel environmentally-friendly preparation technology having good prospect and widely applied to development of intelligent materials and environmental materials.