A chiral <i>C</i><sub>3</sub>-symmetric cubane cluster, [Cu<sub>4</sub>I<sub>4</sub>(TMP)<sub>4</sub>], with enough long Cu–Cu distances to eliminate the presence of Cu–Cu interaction has been synthesized and characterized, which shows simultaneous luminescent thermochromism, solvatochromism, vapochromism, and mechanochromism and is a multiply stimuli-responsive chromic luminescent material. This complex could partly transform into a yellow-emissive bicapped cubane cluster, [Cu<sub>6</sub>I<sub>6</sub>(TMP)<sub>4</sub>(MeCN)<sub>2</sub>], in acetonitrile (MeCN) vapor and solution, which provides some insight into vapochromism and solvatiochromism. This work challenges and makes us reconsider the conventional viewpoint that Cu–Cu interaction...