The study of liquid crystalline assemblies, with an emphasis on biological phenomena, is now accessible using newly developed microdevices integrated with X-ray analysis capability. Many biological systems can be described in terms of gradients, mixing, and confinement, all of which can be mimicked with the use of appropriate microfluidic designs. The use of hydrodynamic focusing creates well-defined mixing conditions that vary depending on parameters such as device geometry, and can be quantified with finite element modelling.We describe experiments in which geometry and strain rate induce finite changes in liquid crystalline orientation. We also demonstrate the online supramolecular assembly of lipoplexes. The measurement of lipoplex orientation as a function of flow velocity allows us to record a relaxation process of the lipoplexes, as evidenced by a remarkable 4-fold azimuthal symmetry. All of these processes are accessible due to the intentional integration of design elements in the microdevices.