Dimethyl (1S,2S,4S,5S)‐4‐allyloxy‐5‐(α‐mannosyloxy)cyclohexane‐1,2‐dicarboxylate (3) was designed as a structural mimic of α(1,2)mannobioside (1). Its synthesis and structural analysis by NMR spectroscopy and molecular modelling are described. The results show that 3, like 1, populates two low‐energy conformations — stacked (S) and extended (E) — that are in fast dynamic equilibrium around the glycosidic linkage. Thus, the data confirm the expectation that the pseudo‐disaccharide can be used as a structural mimic of mannobioside. The mannosidase stability of 3 was found to be significantly higher (sixfold) than that of natural mannobioside. This is a very useful feature of this mimic and is encouraging for its future development. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)