Assessment of exposure to airborne endotoxins has been studied for several years, especially in occupational environments, but a large number of procedures are used for sampling and analysis. This lack of standardization makes it very difficult to compare results and set internationally accepted threshold limit values (TLVs) or occupational exposure limits (OELs) for endotoxin exposure. This paper reviews the methods reported, using advanced bibliographical search techniques: 82 papers published from 2004 to the present were selected to analyze methods for the assessment of human exposure to airborne endotoxins, with particular reference to occupational settings, and to examine their performance and critical points. Only few studies have focused on the standardization of sampling and analysis methods. The European Committee for Standardization Guidelines coincide with the procedures most frequently applied, but this does not guarantee the best results in terms of recovery and reproducibility. The factor that mainly affects endotoxin measurements is the extraction method, the main concern being the presence in the samples of a fraction insoluble in aqueous media. If substantial differences in the proportions of this fraction in different environments are confirmed in the future, the contribution of insoluble endotoxins cannot be neglected.