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We report reversible structural transformation that occurs in two ladder compounds: Cu₂CO₃(ClO₄)₂(NH₃)₆ (<b>1</b>) and Cu₂CO₃(ClO₄)₂(NH₃)₅(H₂O) (<b>2</b>), when they are exposed to gaseous vapors. The ladder structures of both <b>1</b> and <b>2</b> consist of two Cu²⁺ ions and one CO₃²⁻ ion. In <b>1</b>, the Cu²⁺ ions are coordinated by three NH₃ molecules on each side, while those in <b>2</b> are coordinated by three NH₃ molecules on one side, and two NH₃ molecules and one H₂O molecule on the other side. We demonstrated reversible transformation of <b>1</b> and <b>2</b> via the exposure of <b>1</b> to H₂O vapor and the exposure of <b>2</b> to NH₃ vapor using a simple bench-scale method. The minor structural change observed led to a significant difference in physical properties, which we observed using several methods.