We present microstructural investigations of Laves phases AB 2 and structurally related compounds using transmission electron microscopy. Convergent-beam electron diffration in combination with selected-area diffraction has been used to determine uniquely the space group symmetry of the respective phases from very small illuminated regions. In addition stacking faults, domain boundaries, and intergrowth have been studied by HREM images. By electron beam irradiation intermetallic phases have been transformed in-situ into phases of different compositions. Polar intermetallic phases in the systems Ca—Al—Zn, Ba—Al and Ba—Al—Zn, as well as transition metal based Nb-Co phases have been chosen for this case study. In the Ca—Al—Zn system, the C15- and C36-type crystals did not show orderliness but a randomly mixed occupation of the B-net by Al and Zn atoms. Starting from C36, a C15 phase of constant Ca and lower Zn content as well as a new C36 phase with higher Ca content could be synthesized by means of electron beam irradiation. In the case of CaAlZn no ordering of Al and Zn were observed, i.e. , Al and Zn randomly mixed occupy the Cu-site in the CeCu 2 structure type. By electron beam irradiation of CaAlZn, a novel hexagonal phase with a hitherto unknown crystal structure is formed. The crystal structures of Ba 21 Al 40 and Ba 14 Al 22+x Zn 5–x are derived from Laves-type structures by omitting and modifying some of the triangular and Kagom, layers. In the case of Ba 21 Al 40 , intergrowth of motifs from the crystal structures of Ba 3 Al 5 and Ba 4 Al 5 were observed, whereas for Ba 14 Al 22+x Zn 5–x the bulk phase displays a domain structure. Adjacent domains are misoriented by ∼120°, the specific angle resulting from the pseudo-trigonal symmetry of the Ba-net. Therefore, only the (Al,Zn)-net is disordered. No superstructure formation were detected for the three polytypes C36, C15 and C14 in the Nb—Co system. However, TEM images of C36-Nb 1–x Co 2+x reveal a high stacking fault density with intergrowth of stacks of C36 and C15 sequence. When the C15 phase is rich in Nb, stacking faults seem to be more important than for Co-rich C15 phases, whereas stacking faults have seldom been observed for the Co-rich C14 phase.