Pulsed dc dual magnetron sputtering was used for preparation of photocatalytic crystalline TiO2 films. The depositions were performed in an Ar + O2 gas mixture at a total pressure of 0.9 Pa with an oxygen partial pressure of 0.2 Pa. The maximum substrate surface temperature was 160 °C. Both magnetrons operated in the same asymmetric bipolar mode at the repetition frequency of 100 kHz with a fixed 50% duty cycle, but their operations were shifted by a half of the period. Time‐averaged energy‐resolved mass spectroscopy was performed at a substrate position located 100 mm from the targets. A suppression of high‐energy ions in the flux onto the substrate resulted in a strong predominance of the highly photoactive crystalline anatase phase in the TiO2 films.