In this work we present the preparation and structural properties assessment of powder and thin film ternary Ge xAsxSe1-2x (x=0.07¸0.30) chalcogenide glasses by cross-correlating different advanced characterization methods: Scanning Transmission Electron Microscopy (STEM), X-Ray diffraction (XRD) and micro-Raman Spectroscopy investigation methods. STEM and XRD showed the amorphous nature of powder samples and the presence of crystalline domains in the deposited thin films. Moreover, XRD unveiled the intermediate range order (IRO) organization in some of the prepared samples through the appearance of the First Sharp Diffraction Peak (FSDP) in their patterns. The micro-Raman study showed the characteristic Raman signature of Ge_xAs_xSe_1-2x systems and the effects of composition variation. With the increase of Ge and As fractions, a significant increase in the density of the Ge(Se_1/2)₄ structural units has been observed. Based on all these results, we are providing a thorough insight in the structural arrangements of different Ge xAsxSe1-2x compositions, which could enable the control of these systems’ physical properties to make them suitable for different applications, such as phase change memory devices.