The present work introduces microcrystallinity as an elementary building principle in coating systems. New approaches for the fabrication of two microcrystalline material building blocks, two-dimensional graphene and quasi-two-dimensional polyester crystals are presented, which are then combined into a composite.Starting from graphite, few layer graphene with large surfaces are exfoliated by means of direct ultrasound treatment in a butanone (MEK)/water mixture. It turns out that the Hansen Solubility Parameters are a suitable predictor for solvent selection. Functionalized graphene is obtained via the Friedel-Crafts acylation e.g. with sarcosinic acid. This functionalization leads to a considerable increase in dispersibility and exfoliation capability in aqueous systems. Interestingly, by lithium intercalation and subsequent reaction of lithium with water or ethanol, not only graphene layers but also diverse crystal structures of lithium derivatives with uniform construction and sizes can be observed. On the basis of phthalic acids, adipic acid and 1,6-hexanediol, semi-crystalline linear polyester chains are synthesized. Starting from dilute polyester solutions in esters or ketones, ultrathin microcrystalline films are produced by forming ordered crystal lamellae under chain folding during solvent evaporation up to superstructures such as spherulites. The crystal lamellas are well-structured and have uniform sizes in the micrometer range and varying thicknesses from ten to a few hundred nanometers.