The thermal expansion of a number of glassy polymers of interest in dentistry has been studied using a quartz dilatometer. In some cases, the expansion was linear and therefore the coefficient of thermal expansion readily determined. Other polymers exhibited non-linear behaviour and values appropriate to different temperature ranges are quoted. The linear coefficient of thermal expansion was, to a first approximation, a function of both the molar volume and van der Waal's volume of the repeating unit.