Aiming at the construction of novel platform for efficient light harvesting, the precise synthesis of a new family of AIEgen‐branched rotaxane dendrimers was successful realized from an AIEgen‐functionalized 2rotaxane through a controllable divergent approach. In the resultant AIE macromolecules, up to twenty‐one AIEgens located at the tails of each branches, thus making them the first successful example of AIEgen‐branched dendrimers. Attributed to the solvent‐induced switching feature of the rotaxane branches, the integrated rotaxane dendrimers displayed interesting dynamic feature upon the aggregation‐induced emission (AIE) process. Moreover, novel artificial light‐harvesting systems were further constructed based on these AIEgen‐branched rotaxane dendrimers, which revealed impressive generation‐dependent photocatalytic performances for both photooxidation reaction and aerobic cross‐dehydrogenative coupling (CDC) reaction. A novel artificial light‐harvesting system based on AIEgen‐branched rotaxane dendrimers has been successfully constructed which displayed impressive generation‐dependent photocatalytic performances for both photooxidation reaction and aerobic cross‐dehydrogenative coupling reaction.