A new and facile technique for the preparation of ZnO@TiO₂ core–shell nano/micro sphere structures from tetrazolate ligand, (1,3-bis(tetrazol-5-ylmethyl)benzene (btb)), was addressed. Via a solvent-induced precipitation method, nanoparticles of TiO₂ bearing Rhodamine B were encapsulated into the Zn(btb) hollow spheres. The resulting polymeric carriers were characterized by SEM, HRTEM, EDS and XRD analyses and subsequently were used as precursors for the preparation of crystalline zinc oxide mineral spheres containing TiO₂ species using a calcination route.