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This work examines the nature and dynamics of the polymorphic behaviour of long-chain saturated monoglycerides (MGs) in hydrogels and in structured oil-in-water emulsions. The stability of the metastable -gel phase has been successfully improved by using certain co-emulsifiers, processing parameters, and storage conditions. A highly stable MG -gel phase in turn allows for enhanced performance of MG emulsifiers in food products. The novel application of MG-structured emulsions as cosmetic creams has also been investigated. Its potential as an alternative "green", petroleum-free cosmetics is demonstrated through rheological and skin hydration tests.