Solid-state conversion of NaI coordination polymer nanostructure, synthesized by sonochemical procedure, to TlI coordination polymer has been observed upon liquid-assisted mechanochemical reaction of [ Na2TP]n (1) ( H2TP = terephthalic acid), with TlNO3. During this conversion, ion exchange process of Na(I) with Tl(I) was occurred and [ Tl2TP]n (2) was synthesized. The X-ray diffraction (XRD) pattern of 2 after mechanochemical reaction of it with NaNO3 indicated that this transformation is irreversible. Compounds 1 and 2 were characterized by IR spectroscopy, X-ray powder diffraction (XRD), elemental analysis, thermogravimetric and differential thermal analyses and scanning electron microscopy.