Glasses frequently reveal structural relaxation that leads to changes in their physical properties including enthalpy, specific volume, and resistivity. Analyzing the short‐range order (SRO) obtained from electron diffraction by transmission electron microscopy (TEM) in combination with Reverse‐Monte‐Carlo (RMC) simulations is shown to provide information on the atomic arrangement. The technique elaborated here features several benefits including reliability, accessibility, and allows for obtaining detailed structural data quickly. This is demonstrated with a detailed view of the structural changes in the as‐deposited amorphous phase change material (PCM) GeTe. The data show a significant increase in the average bond angle upon thermal treatment. At the same time the fraction of tetrahedrally coordinated Ge atoms decreases due to an increase in octahedrally distorted and pyramidal motifs. This finding provides further evidence for the atomic processes that govern structural relaxation in amorphous GeTe and other PCMs. A thorough literature review finally unveils possible origins of the large discrepancies reported on the structure of amorphous GeTe. Structure function ϕ(q) and Pair Distribution Function G(r) of the technologically relevant phase‐change‐material GeTe are obtained by TEM diffraction. Reverse‐Monte‐Carlo simulations based on this structural data reveal atomic rearrangement processes, shedding light on structural relaxation that leads to resistance drift in GeTe. The here elaborated method is capable of reliably reproducing structural models obtained from large scale synchrotron‐facilities as shown for several materials like amorphous silica.