Phase-selective growth of TlBa2Ca2Cu3O9−x films is greatly enhanced by annealing chemical vapor deposition derived BaCaCuO(F) precursor films in the presence of TlF. Nucleation of superconducting phases (≥840 °C under O2) progresses in the order 2212 → 2223 → 1212 → 1223. Annealing at 855 °C results in well-defined platelet grains, a significant number of which are a-axis oriented. Residual fluoride is not detectable at any stage of the annealing process. Thin films synthesized by TlF annealing differ markedly from films processed in the presence of Tl2O3 with Tc = 103 K and Jc > 105 A/cm2 (5 K, 4.5 T).