Agricultural workers rely on chemically protective gloves for protection from dermal exposure to insecticides. In Australia the most widely used gloves are manufactured from polyvinyl chloride or nitrile butadiene rubber. During insecticide application splashes and spills frequently occur on the external surfaces of gloves which may compromise the integrity of the membrane. Interaction of two organophosphate insecticides, chlorpyrifos (Lorsban 500 EC(R)) and diazinon (Jetdip(R)), with glove surfaces was investigated in laboratory conditions. The external surface of gloves was treated with concentrated insecticides for one minute and diluted and concentrated insecticides for 24, 36 and 48 hours and later examined by environmental scanning electron microscopy. Two classes of defects, cavities and convexities, were evident in the polyvinyl chloride gloves following all treatments, whereas cracking was significant in the nitrile butadiene rubber gloves after 24 hours. In addition, X-ray energy-dispersive microanalysis was used to evaluate chemical changes on the glove surfaces. Phosphorus and sulfur were useful indicators for organophosphate retention over specific time frames. Results corroborated the need for more robust chemically protective gloves to be developed for routine agricultural use.