Abstract <p>Doping rare-earth element into sulfur cluster can significantly increase the stability and induce unique optical activity. On this basis, a series of neutral and anionic cerium-sulfur clusters Ce₆S_<i>n</i>^0/− (<i>n</i> = 1 − 11) are designed, and their structural evolution is revealed by global search techniques combined with PBE0 density functional theory. The Structural growth is observed in three stages: at 1 ≤ <i>n</i> ≤ 8, to gradually create the Ce₆S₈ Chevrel phase structure; at <i>n</i> = 9, a transitional structure emerges; and at 10 ≤ <i>n</i> ≤ 11, S atoms are adsorbed on the triangular prism Ce₆. In addition, various properties including, relative stability, energy gap, (hyper)polarizability and excitation behavior are analyzed. The Ce₆S₇⁻ nanocluster exhibits outstanding linear and nonlinear optical activity (<i>β</i>_total = 9.66 × 10⁴ a.u.), wide absorption range and high exciton binding energy, making it a promising building block for next-generation optoelectronic nanodevices.</p> Graphical abstract <p></p>