The class of fatty alcohol alkoxylates describes surfactants that are synthesised by reaction of fatty alcohols with alkoxides such as ethylene oxide or propylene oxide or a combination of both as copolymers. Such alkoxylates are used, for example, as nonionic surfactants in home and industrial cleaning and washing agents. Chemical characteristics of such alkoxylate copolymers, for example the degree of alkoxylation, the arrangement of building blocks (random or block polymerisation), the type of the starter, and endcapping, play an important role in application behaviour. The analysis of these characteristics is challenging because in many cases such copolymers have high polydispersity and a large number of constitutional isomers depending on the degree of alkoxylation. Furthermore, the alkoxylates often occur in a complex multicomponent matrix. Here we present a method for characterization of silylated fatty alcohol alkoxylates in the low-molecular-weight range by means of comprehensive two-dimensional gas chromatography-mass spectrometry with electron impact and chemical ionisation. This method also enables detailed analysis of the alkoxylates in a complex matrix such as modern detergents.