This paper describes a topochemical synthetic approach to Co2+-Fe3+ layered double hydroxides (LDHs). Micrometer-sized hexagonal platelets of brucite-like Co2/3Fe1/3(OH)(2) were first prepared by a homogeneous precipitation of an aqueous solution of divalent cobalt and ferrous ions through hexamethylenetetramine (HMT) hydrolysis under a nitrogen gas atmosphere. A subsequent oxidative intercalation process, by the action of iodine (I-2) in chloroform (CHCl3), transformed the precursory brucite-like Co2+-Fe2+ hydroxides into hydrotalcite-like Co2+-Fe3+ LDHs, in which the oxidization of Fe2+ into Fe3+ induced positive charges to the octahedral hydroxyl layers while anions (I-) were intercalated into the interlayer space. Co2+-Fe3+ LDHs inherited the high crystallinity and hexagonal platelet morphology from their brucite-like precursor due to the topotactic nature of the transformation, which was verified by abundant microscopic and spectroscopic characterizations. After a normal ion-exchange process, Co2+-Fe3+ LDHs accommodating perchlorate anions were exfoliated into unilamellar nanosheets in formamide by an ultrasonic treatment.