Design of nanostructured catalytic materials plays a strategic role in the synthesis of organic compounds with outstanding physicochemical properties. In this regard, titanium dioxide nanostructures doped with a single metal, namely, nickel and copper, were successfully prepared by a sol-gel method, and their phase structures, elemental compositions and morphologies were extensively characterised. In particular, X-ray diffraction (XRD) diffractograms and Raman spectra mainly revealed a rutile-phase structure for Cu-doped TiO2 and a biphasic anatase–rutile structure for Ni-doped TiO2. In addition, catalytic activities of Cu- and Ni-doped titanium dioxide nanostructures were evaluated for the synthesis of pyridopyrimidine derivatives from sulphur intermediates by the Liebeskind–Srogl reaction under UV illumination. Under the optimized reaction conditions, the target compounds were obtained in a yield of up to 87% by using the Cu-doped TiO2 catalyst and with a slightly lower yield of up to 79% for Ni-doped TiO2 in 12 h. Overall, the catalytic activity of Cu-doped TiO2 was greater than that of Ni-doped TiO2.