High-entropy layered oxides (HELOs) represent a very promising class of next-generation battery cathodes, combining the well-studied properties of layered cathode materials such as LiCoO2 with the chemical tunability and stability of high-entropy materials. HELO materials often form particles with complex defects and domain structures, complicating accurate characterization of structure and cation mixing. Understanding disorder and order in HELO materials is necessary for understanding their performance and utility as cathodes. Here we demonstrate the characterization of the HELO Li1.5MO3-δ (M = Mn, Al, Fe, Co, Ni), wherein X-ray powder diffraction, transmission electron microscopy imaging, and electron diffraction patterns are analyzed to reveal the presence of ordering in the HELO, with imaging and diffraction simulation employed to compare experimental results to atomic modeling. Without rigorous characterization at the atomic scale, important features such as defect ordering can be easily overlooked and therefore remain unconsidered when interpreting experimental results.