Yttria (Y2O3) films were deposited on stainless steel substrates from ethylenediaminetetraacetic·yttrium·hydrogen (EDTA·Y·H) complexes by flame spraying. The gas mixtures of acetylene-oxygen (C2H2-O2) or hydrogen-oxygen (H2-O2) were used for the combustion flame and the effects of the combustion gas species on Y2O3 films were investigated. Experiments revealed that the particles propelled in the H2-O2 flame had lower temperature and higher velocity compared with the particles in the C2H2-O2 flame. The existence of Y2O3 crystalline phases and complete decomposition of the EDTA·Y·H were confirmed. The porosity of the film was 25% when the H2-O2 flame was used and 32% when the C2H2-O2 flame was used. In addition, the Y2O3 films showed excellent adherability in tape tests. The H2-O2 flame is thus considered suitable for fabricating dense Y2O3 films.