Bi12(GaxBi1−x)O19.5 (BGaO) films with thickness in the range 100–1000 nm have been deposited on (100) Y-stabilized zirconia (YSZ) and (100) Bi12GeO20 (BGO) substrates using a KrF excimer pulsed laser and polycrystalline targets with composition x=0.63–0.72. The laser power density threshold for ablation of the targets has been determined to be J0=4.8 J/cm2. A deposition rate of 0.03 Å/pulse was found for the substrate-target distance (6 cm) and laser fluence (J=7 J/cm2) used. Transparent and crystalline films were obtained heating the substrate in the 450–550 °C range under 1.5×10−1 mbar of oxygen pressure. Films deposited on hot substrates have a Ga stoichiometry x=0.5 but a Bi content slightly lower than that corresponding to sillenite. Films deposited on YSZ show preferential orientation. From the x-ray diffraction results and the comparison of the ionic distributions, it has been concluded that the most likely orientation between both lattices is 〈310〉{130}BGaO∥〈011〉{100}YSZ. A {100}BGaO∥{100}BGO epitaxy has been inferred from Rutherford backscattering analysis. On both substrates the films behave as step waveguides with refractive index close to the value determined in bulk BGaO.