When engineering lipid membranes for applications, it is essential to characterize them to avoid artifacts introduced by manipulation and the experimental environment. Wide-angle X-ray scattering is a powerful structural characterization tool for well-ordered lipid systems. It reveals remarkable differences in rotational order parameters for samples prepared in different ways. New data and perspectives are presented here for multilamellar systems that support and extend the characterization work on unilamellar systems that is reported by Watkins et al. in this issue of ACS Nano.