Saturn's moon Enceladus harbours a global water ocean, which lies under an ice crust and above a rocky core. Through warm cracks in the crust a cryo-volcanic plume ejects ice grains and vapour into space that contain materials originating from the ocean. Hydrothermal activity is suspected to occur deep inside the porous core, powered by tidal dissipation. So far, only simple organic compounds with molecular masses mostly below 50 atomic mass units have been observed in plume material. Here we report observations of emitted ice grains containing concentrated and complex macromolecular organic material with molecular masses above 200 atomic mass units. The data constrain the macromolecular structure of organics detected in the ice grains and suggest the presence of a thin organic-rich film on top of the oceanic water table, where organic nucleation cores generated by the bursting of bubbles allow the probing of Enceladus' organic inventory in enhanced concentrations.