High resolution electron microscopy and scanning electron microscopy were used to determine the distribution of intergranular films and microvoids in Synroc C. Diffraction contrast derived from these films, which were 1–3 nm thick, showed then to be ill-defined crystallographically, and they may be described as glassy. Pores were usually several micrometers in extent and occurred principally in rutile-rich areas. The chemical composition of these structural features was obtained using analytical transmission electron microscopy, secondary ion mass spectrometry, x-ray photoelectron spectroscopy and scanning Auger microscopy. Within intergranular films, elemental enhancement of cesium, sodium, potassium and aluminium, and possibly silicon and molybdenum was observed. Enhancement of cesium, sodium, phosphorous, aluminium and silicon was found at triple points. Fracture faces preferentially expose grain boundaries, and dissolution of these surfaces proceeds rapidly at ambient temperatures. During the fabrication of Synroc C, microvoids trap cesium vapour, and after cooling this condenses onto pore surfaces. Recognition of the (simulated) waste species which segregate at grain boundaries and pores, permitted the reinterpretation of published leach data for monolithic and crushed Synroc C.