Hygroscopic and thermal expansion behavior of advanced polymers is investigated when subjected to combined high temperature and moisture conditions. An enhanced experimental–numerical hybrid procedure is proposed to overcome the limitations of the existing methods when used at temperatures above the water boiling temperature. The proposed procedure is implemented to measure the hygrothermal strains of three epoxy molding compounds and a no-filler underfill over a wide range of temperatures including temperatures beyond the water boiling temperature. The effects of moisture content on the glass transition temperature (Tg) and coefficient of thermal expansion (CTE) are evaluated from the measurement data. A formulation to predict the Tg change as a function of moisture content is also presented.