In this work, the conditions for the synthesis of open vase-like microcapsules with a size of 1–5 μm and 20–40 nm walls of NiFe0.3(OH)x layered double hydroxide were studied. These microcapsules were obtained by the rapid hydrolysis of microdroplets of a solution of a mixture of NiSO4 and FeSO4 salts at the surface of an alkali solution. A hypothetical model of successive chemical processes occurring at the interface during synthesis is presented. The features of the “rim” formation around each microcapsule hole from the wall material with a peculiar nozzle-like shape are noted. These microcapsules can be transferred to the surface of a nickel foil using the Langmuir–Schaefer (LS) method. During the transfer process, they are fixed to the surface in an oriented position with a “rim” that contacts the nickel surface. It was established that electrodes made of such a foil with a layer of microcapsules exhibit active electrocatalytic properties in the oxygen evolution reaction during the electrolysis of water in an alkaline medium.