This paper describes the synthesis of TiO2-SnO2 heterostructures and their application to water decontamination based on the photodegradation of Rhodamine B (RhB). The heterostructures were fabricated through two different routes, a hydrolytic sol gel and the polymeric precursor method, both of which induced the growth of SnO2 on commercial TiO2. The results show that the heterostructures presented higher photoactivity behaviors than commercial TiO2 nanopowders. The achievement of homogeneity during phase formation (i.e., of the SnO2 dispersion over the TiO2 nanoparticles) was a key parameter for obtaining higher photocatalytic activities per unit area. The main degradation mechanism was correlated with the process of rad OH radical generation, which was related to the concentration and nature of the surface hydroxyl groups. Accordingly, the polymeric precursor method was shown to be more adequate for dispersing higher amounts of SnO2 in comparison with the hydrolytic sol gel method. Additionally, the polymeric precursor method delivered higher proportions of bonded surface hydroxyl groups, which were responsible for radical formation; in contrast, the hydrolytic sol gel method demonstrated the highest amount of adsorbed water.