The heterogeneous photocatalytic oxidation of rhodamine B in aqueous solution containing pure or zinc (iron)-doped titania films has been studied. N-deethylation of rhodamine B was accelerated by iron(III) and zinc(II) doping as compared with pure titania film. It is shown that improvement of electron transfer from dye molecules to the film may be responsible for the high N-deethylation rate for iron-doped (0.5 mol%) film, while for zinc-doped (20 mol%) film, high surface roughness may be the main reason. In addition, both iron and zinc doping brought a new shallow trap to the intragap meaning that the surface defects had increased after doping; this is a possible reason doped films present relative low photoreactivity to catalyze the direct degradation of dye molecules.