Plastics can be found in all ecosystems across the globe. This type of environmental pollution is important, even if its impact is not fully understood. The presence of small plastic particles at the micro- and nanoscales is of growing concern, but nanoplastic has not yet been observed in natural samples. In this study, we examined four size fractions (meso-, large micro-, small micro-, and nanoplastics) of debris collected in the North Atlantic subtropical gyre. To obtain the nanoplastic portion, we isolated the colloidal fraction of seawater. After ultrafiltration, the occurrence of nanoscale particles was demonstrated using dynamic light scattering experiments. The chemical fingerprint of the colloids was obtained by pyrolysis coupled with gas chromatography–mass spectrometry. We demonstrated that the signal was anthropogenic and attributed to a combination of plastics. The polymer composition varied among the size classes. At the micro- and nanoscales, polyvinyl chloride, polyethylene terephthalate, polystyrene and polyethylene were observed. We also observed changes in the pyrolytic signals of polyethylene with decreasing debris size, which could be related to the structural modification of this plastic as a consequence of weathering.