Structural investigations on amorphous AsxTe1−xthin films and bulk glass samples have been performed as a function of composition ′x′ and heat treatment. Spectra of amorphous AsxTe1−xin the composition range 0.10?×?0.57 show quadrupole doublets, characterized by fairly well defined splittings. Data obtained for a total of six compositions in the specified range, show that the quadrupole splitting (QS) increases smoothly as ′x′ decreases suggesting the lack of chemical ordering in this system. Kinetics of crystallization atx=0.30 and 0.50 were systematically investigated. The amorphous to crystalline transformation in the Te rich phase (x=0.30) leads to Te in two chemical evironments, Te metal and monoclinic As2Te3. In the As rich phase (x=0.50), the process of crystallization reveals intermediate phases.