The quantity and composition of litter at riversides and in the surface waters, as well as the occurrence of illegal dumping sites, were studied along four rivers in Chile. Data generated by volunteers were compared to the results from a professional survey, using an identical protocol. Litter was found in considerable quantities at the riversides and in the surface waters at all the sites investigated. A generalized linear mixed model analysis showed that the recorded litter densities did not differ between volunteers and professionals, even after controlling for river, site, or distance between sampling locations, demonstrating that the volunteers successfully applied the sampling protocol. Differences occurred with respect to litter composition, which is most likely due to difficulties in the classification of litter items and particles and to the underestimation of litter present in surface water samples. Even though this study was only conducted at a small number of rivers and sites, a comparatively consistent pattern of direct and intentional litter deposition at riversides was recorded, highlighting that river basins require more protection. The results also show that the citizen science approach can be a suitable means for more extensive litter surveys at riversides and in other natural environments.