The chiral 3-fold interpenetrating diamondoidlike Cu(II)-containing coordination polymer [Cu(2,5-bis(4-pyridyl)-1,3,4-oxadiazole)2(H2O)](ClO4)2]n (1a) is reported. It undergoes a temperature-driven reversible single-crystal-to-single-crystal structural transformation between room- (293 K, 1a) and low-temperature (150 K, 1b) forms.