Personal protective equipment (PPE) should only be used as a control measure when other measures are inappropriate or are inadequate by themselves. The person undertaking a risk assessment must exercise his or her judgment to take into account the protection afforded by the PPE. There is, therefore, considerable scope for differences in approach and it would seem sensible to eliminate these differences and ensure consistency, where possible, by reaching agreement on the attenuating effect of PPE. However, there is growing evidence that the levels of protection indicated by laboratory-based tests may not be achieved in real use situations. Studies of workplace protection suggest that the spread of contaminants inside protective clothing, including gloves, is commonplace and significant. Insufficient attention may have been paid to the effect of factors such as temperature differentials on the permeation of chemical agents through protective materials. To investigate this, a test cell was designed and built to measure the breakthrough times and subsequent permeation rate of solvents through glove materials where the temperature inside and outside the glove was representative of those that can occur in the workplace. Two chemical solvents were tested against two different glove materials at three different temperature conditions. The differences between the breakthrough times and permeation rates were measured and compared to manufacturer's test data. The practical implications are considered for risk of health and safety to the wearer.