Plasmonic superstructures offer broad prospects in photothermal catalysis, yet their controllable synthesis remains a challenge. Here, a controlled synthesis method for Cu‐Ru plasmonic superstructures via a one‐step polyol reduction process is presented, where Cu nanoparticles serve as the core, while the shell is formed from Ru nanoclusters. Through a comprehensive investigation of the growth mechanism, precise control over the composition and size of the superstructures is achieved. Finite‐difference time‐domain simulations and photothermal conversion experiments demonstrated that the optimized Cu3Ru1 superstructures possess strong light absorption capabilities and efficient photothermal conversion performance. These properties are effectively utilized in the photothermal recycling of waste polyethylene and polyethylene terephthalate, marking a significant advance in employing Cu‐based plasmonic materials for sustainable catalytic technology.