TiO2nanoparticles were synthesized by laser pyrolysis from TiCl4vapor in air in the presence of ethylene as sensitizer at different working pressures (250–850 mbar) with and without further calcination at 450 °C. The obtained powders were analyzed by energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, X-ray diffractometry, and transmission electron microscopy. Also, specific surface area and photoluminescence with optical absorbance were evaluated. By varying the synthesis parameters (especially the working pressure), different TiO2nanopowders were obtained, whose photodegradation properties were tested compared to a commercial Degussa P25 sample. Two series of samples were obtained. Series “a” includes thermally treated TiO2nanoparticles (to remove impurities) that have different proportions of the anatase phase (41.12–90.74%) mixed with rutile and small crystallite sizes of 11–22 nm. Series “b” series represents nanoparticles with high purity, which did not require thermal treatment after synthesis (ca. 1 atom % of impurities). These nanoparticles show an increased anatase phase content (77.33–87.42%) and crystallite sizes of 23–45 nm. The TEM images showed that in both series small crystallites form spheroidal nanoparticles with dimensions of 40–80 nm, whose number increases with increasing the working pressure. The photocatalytic properties have been investigated regarding the photodegradation of ethanol vapors in Ar with 0.3% O2using P25 powder as reference under simulated solar light. During the irradiation H2gas production has been detected for the samples from series “b”, whereas the CO2evolution was observed for all samples from series “a”.