The azobenzene-functionalized Fischer carbene complexes 5a − c have been synthesized using organozinc compounds generated in situ by lithium/zinc exchange. Aminolysis of the 4‘-substituted methoxycarbene complexes 5a and 5b with an amino sugar derivative yields aminocarbene complexes, which can be deprotected under mild conditions to give the amphiphilic azobenzene Fischer carbene complexes 1a and 1b. The spectroscopic properties and the aggregation behavior of the target compounds in the gas phase have been studied using ESI-MS.