High‐temperature superconducing Tl‐Ca‐Ba‐Cu‐O (TlCaBaCuO) thin films were fabricated by rf magnetron sputtering on strontium titanate (SrTiO3) substrates. Thin films of 0.5–0.7‐&mgr;m thickness were deposited by pure argon sputtering from a single composite powder target of Tl2Ca2Ba2Cu3Oxat an rf power of 250 W and a pressure of 5 mTorr. As‐deposited thin films were sintered and annealed in a thallium‐rich ambient to obtain superconductivity with a zero resistance temperature (Tc0) at 107 K. X‐ray diffraction results showed highlyc‐axis oriented films with Tl2Ca2Ba2Cu3Ox(2223) and Tl2Ca1Ba2Cu2Ox(2122) phases present. Auger electron spectroscopy survey and depth profiles were performed to determine the compositional uniformity and impurity contents of the thin films. X ray photoelectron spectroscopy high‐resolution spectra were obtained at the surface, in the bulk, and near the interface with the substrate. Our XPS results support two possible mechanisms for the creation of holes in the TlCaBaCuO compound: (1) partial substitution of Ca2+for Tl3+and (2) charge transfer from Tl3+to the CuO layers resulting in a valence of Tl between +3 and +1 states and the creation of holes in the CuO layers. In addition, a wet chemical etching process was developed for patterning the as‐deposited TlCaBaCuO thin films. A 125‐&mgr;m‐wide line was formed using standard photolithography and wet chemical etching which, after heat treatments, showed superconductivity with aTc0of 80 K.