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In recent years, the development of nanotechnology has led to an increase in production and use of engineered nanomaterials. The subsequent increased risk of exposure has raised growing concern about the potential adverse health effects resulting from exposure to nanomaterials. Therefore, in order to protect the health of occupationally exposed subjects, it is necessary to develop and implement an adequate process of risk assessment. In this context, the exposure assessment by conducting environmental and biological monitoring is a key element. However, the limited and fragmented understanding of the toxicokinetics and toxicodynamics of engineered nanomaterials currently hinder the practical application of these evaluation tools. The aim of this review is to identify the critical issues that prevent the full implementation of environmental and biological monitoring of nanomaterials in workplaces to provide useful guidance to the development of validated exposure assessment strategies.