The sea surface microlayer and its thickness are theoretically analyzed. A multiple-layer model of the sea surface microlayer is proposed. Through in situ and laboratory imitation experiments using glass plate, rotating drum, screen, and funnel samplers, the relationships between pH, surface tension, the concentrations of dissolved trace metals Cu and Pb, phosphate, and particulate and sampling thicknesses are carefully investigated. The apparent sampling thickness of the sea surface microlayer is determined to be 50 +/- 10 mu m, which is basically consistent with the mean thickness of the liquid boundary film in the models of gas exchange across the sea surface.