Chemically synthesized brookite titanium dioxide (TiO2) nanorods with average diameter and length dimensions of 3–4ánm and 35–50ánm, respectively, were deposited by the matrix-assisted pulsed laser evaporation technique. Aátoluene nanorod solution was frozen at the liquid-nitrogen temperature and irradiated with a KrF excimer laser (λ=248ánm, τ=20áns) at the repetition rate of 10áHz, at different fluences (25 to 350ámJ/cm2). The deposited films were structurally characterized by high-resolution scanning and transmission electron microscopy. 〈100〉 single-crystal Si wafers and carbon-coated Cu grids were used as substrates. Structural analyses evidenced the occurrence of brookite-phase crystalline nanospheres coexisting with individually distinguishable TiO2 nanorods in the films deposited at fluences varying from 50 to 350ámJ/cm2. Nanostructured TiO2 films comprising only nanorods were …