Bi-crystals and tri-crystals of a nominal Fe-3% Si (wt%) of well-defined orientations have been grown using a floating-zone technique with optical heating. The manufacture of these unique crystals and the preparation technique involved in harvesting thin foils from specific locations for transmission electron microscopy are described in detail. In particular, the grain boundary triple junction has been extracted from the tri-crystal and examined in high-resolution aberration-corrected FEG-STEM instruments. To achieve the necessary resolution, the foils have to be uniformly thin, in the range 50-100 nm over large areas of the specimen. For ferromagnetic materials, there are further challenges arising from the magnetic field interaction, with the electron beam placing significant demands on the aberration correction system. One way to minimise this interaction is to reduce the total mass of magnetic material. To achieve this, an in situ focused ion beam lift-out technique has been combined with an additional precision ion-polishing stage to reproducibly provide thin-foil specimens suitable for high-resolution EELS and EDX analysis. Examination of the foils reveals that the final precision ion-polishing stage removes residual damage arising from the use of focused ion beam milling procedures.