Barium sodium niobate (BSN) optical waveguide films were grown on potassium titanyl phosphate (KTP) substrate by pulsed laser deposition (PLD). X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray pole spectroscopy, and X-ray photoelectron spectroscopy (XPS) showed that the as-grown BSN films are epitaxially smooth, fine-particled and show small constituent deviation. Both m lines of the waveguided TE and TM modes were recorded. Lattice match between the BSN(110) and both the KTP(001) and KTP(100) planes is examined with mismatch less than 3%. Effective refractive indices as a function of incident wavelength and order of the waveguided modes are studied. A phase matching relationship of k(1)−2k(0)=0 is established between the first-order and fundamental modes in the BSN/KTP waveguided system. Effective thicknesses for TE and TM modes were obtained to be equal to 0.76 and 0.72 μm, respectively, larger than the thickness of the as-grown BSN film of 0.60 μm. A constituent ratio of Ba:Na:Nb in the BSN film measured was equal to 2:0.82:5.14, slightly deviating from the stoichiometric ratio of 2:1:5, which is attributed to higher relative asymptotic velocity for Nb species and higher evaporation pressure for Na species. Finally, the main factors affecting quality of the as-grown BSN films are also discussed.