Molecular iodine was intercalated from nonaqueous solution into microsized ZnAl-layered double hydroxide (LDH) in the iodide form, generating the I-3(-)/I- redox couple into the interlayer region. Chloroform, ethanol, acetonitrile, or diethyl ether were used as solvents to dissolve the molecular iodine. The intercalation compounds were characterized by thermogravimetric analysis, X-ray powder diffraction, UV-vis spectroscopy, and scanning and transmission electron microscopy. The stability of iodine-solvent adducts and the iodine concentration affected the LDH iodine loading, and samples with I-2/I- molar ratio ranging from 0.14 to 0.82 were prepared. Nanosized, well dispersible LDH, synthesized by the urea method in water-ethylene glycol media, were also prepared and successfully functionalized with the I-3(-)/I- redox couple applying the conditions optimized for the micrometric systems.