Dermal exposure assessment explores the dynamic interaction between environmental contaminants and the skin. The measure of skin exposure can be made using direct methods (interception techniques, removal techniques from skin, in situ detection) or indirect methods (biological monitoring, removal techniques from surfaces). The selection of the appropriate sampling method will depend on a range of factors (the sampling objectives, the compartment or transport process of interest, the nature of the agent and the analytical methods to be used) and should be part of a coherent and documented sampling strategy. In this work we describe the processes leading to exposure, in relation to the presence of clothing or protective garments, discuss on factors that influence skin penetration (both the physiologic characteristics of the skin and the physico-chemical nature of the compound that comes into contact with the skin) with the purpose to assess and manage the risk of skin exposure.