The symmetric dimeric complex [Cu(mu(2)-hep)(TFA)(H2O)](2) (1) has been synthesized from 2-(2-hydroxyethyl)pyridine (hep-H), trifluoroacetic acid (TFA-H), and copper acetate in a 95:5 (v/v) MeOH-H2O mixture at 298 K. Each Cu-II ion in 1 is linked with two mu(2)-alcoholic oxygen atoms and one pyridine nitrogen atom of hep, and the other two coordination sites are occupied by the oxygen donors of TFA and H2O. At room temperature, the blue single crystals of 1 transform to the green single crystals of a tetrameric complex, [Cu-4(mu(3)-hep)(2)(mu(2)-hep)(2)(mu(2)-TFA)(2)(TFA)(2)] (2), in presence of alcoholic vapor. The facile single crystal-to-single crystal (SCSC) transformation of 1 to 2 is accompanied by the removal of coordinated H2O molecules in 1 and concomitant formation of four new covalent bonds, two Cu-O(mu(3)-hep) and two Cu-O(u(2)-TFA). The SCSC transformation of 1 to 2 is selective to the alcoholic vapor; the exposure of single crystals of 1 to heat or light or in vacuum has resulted in an immediate loss in crystallinity.