The work focuses on exploring the effect of the concentration of Sm dopant (0.2–0.6 at.%) on structural, optical and photocatalytic properties of the spin coated titania based thin films annealed at different temperatures. The optical interpretation involves the influence of Sm doping on optical constants and luminescence behaviour of the samples. The comprehensive work on optical bandgap, Urbach energy and electron-phonon interaction strength was conducted for Sm doped samples. The optical band gap was found to increase with the increasing concentration of Sm, but decreased with high temperature annealing. Using ellipsometry measurement, refractive index of the samples was obtained. The orbital level information was gathered using X-Ray Photoelectron Spectroscopy (XPS) study with a special emphasis on the evolution of physico-chemical properties as function of Sm doping. The XPS study confirms the presence of Sm in the titania host material and it helped in estimating defects induced by Sm doping. The photocatalytic study of Sm doped titania thin films was carried out by using methylene blue (MB) and Rhodamine B (RhB) dye and we have found an enhanced photocatalytic activity for the 0.4 at.% Sm doped samples.