The invention belongs to the technical field of smart materials and environmental materials, and particularly relates to a multi-responsive dendronized polymer prepared by initiating thiol-ene click reaction through visible light and a method of the multi-response dendronized polymer. A mercapto-based compound and an acrylate-based compound are taken as monomers, and the thiol-ene click chemical reaction and a visible light-initiating free radical polymerization method are used for successfully synthesizing the intelligent multi-responsive dendronized polymer. The preparation method has the main advantages of environment protection, simple operation, mild conditions and efficient reactions, organic acids and alkali promoters are no longer required, the catalyst cost is saved, and the problem of residual metal catalysts is solved. The prepared and synthesized multi-responsive dendronized polymer exhibits excellent photosensitivity behavior, the photosensitivity behavior has pH and redoxdependence, and the preparation method is a promising novel green preparation technology which can be widely used in the development of smart materials and environmental materials.