Polymeric composite based underfill materials, with well-controlled coefficient of thermal expansion (CTE) are critical to flip-chip and other advanced high-density integrated circuit packaging technologies. The use of underfills beneath the flip-chip integrated circuits leads to an increase in reliability by reducing the strain on the solder bumps during thermal cycling imposed by the CTE mismatch between the chip and substrate. A fundamental understanding of the composite CTE of underfill materials is critical to the manufacture of high performance underfill materials and is critical to market expansion of flip-chip technology for high density packaging applications. This work presents a novel model for predicting the effective CTE of underfills and other polymeric composite materials by considering the effect of an interphase zone surrounding the filler particles in a polymer matrix. A microscopic model is also introduced for the volume fraction of the interphase as a function of filler concentration as well as filler–filler overlapping. The CTE model resolves several conflicts regarding the effect of filler concentration, filler size and filler–polymer interaction on the effective CTE of underfill and other polymeric composite materials. The results are demonstrated to be critical for accurate flip-chip reliability predictions based on finite-element and other modeling techniques.