Sewage effluent input and population were chosen as predictors of microplastic presence in sediments at four sites in the River Thames basin (UK). Large microplastic particles (1 mm–4 mm) were extracted using a stepwise approach to include visual extraction, flotation and identification using Raman spectroscopy. Microplastics were found at all four sites. One site had significantly higher numbers of microplastics than other sites, average 66 particles 100 g− 1, 91% of which were fragments. This site was downstream of a storm drain outfall receiving urban runoff; many of the fragments at this site were determined to be derived of thermoplastic road-surface marking paints. At the remaining three sites, fibres were the dominant particle type. The most common polymers identified included polypropylene, polyester and polyarylsulphone. This study describes two major new findings: presence of microplastic particles in a UK freshwater system and identification of road marking paints as a source of microplastics.This study is the first to quantify microplastics of any size in river sediments in the UK and links their presence to terrestrial sources including sewage and road marking paints.