A novel methodology has been developed for the preparation of amorphous semiconductor samples for use in transmission extended x-ray absorption fine structure (EXAFS) measurements. Epitaxial heterostructures were fabricated by metal organic chemical vapour deposition (group III-Vs) or molecular beam epitaxy (group IVs). An epitaxial layer of ∼2 μm thickness was separated from the underlying substrate by selective chemical etching of an intermediate sacrificial layer. Ion implantation was utilised to amorphise the epitaxial layer either before or after selective chemical etching. The resulting samples were both stoichiometric and homogeneous in contrast to those produced by conventional techniques. The fabrication of amorphous GaAs, InP, In0.53Ga0.47As and SixGe1-x samples is described. Furthermore, EXAFS measurements comparing both fluorescence and transmission detection, and crystalline and amorphised GaAs, are shown.