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A series of amide‐linked surfactants from methyl glucoside was synthesized and investigated for their potential use as water‐in‐oil emulsifiers. The synthetic concept combined a nucleophilic substitution approach with a Staudinger coupling of the intermediate azide. Both straight and Guerbet‐type branched fatty acids ranging from C8 to C16 were applied. All surfactants exhibited very high Krafft temperatures, which were related to the amide linkage and exclusively formed the hexagonal H1‐phase. The Guerbet C16 surfactant enabled the formation of a stable water‐in‐oil gel at ambient temperature, which, however, required heating to form the corresponding fluid emulsion.

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