Negative thermal expansion materials with open frame structure were easy to undergo phase transformation under high thermal mismatch stress. In this work, a large amount of γ-phase was found in ZrW2O8/Al composite, presenting great fluctuations. Based on the temperature-dependent Raman spectroscopy and theoretical calculation, the accurate heat-treatment temperature was used to eliminate γ-phase and low thermal expansion composite without abnormal expansion was obtained. The Raman frequency shift caused by the thermal stress was quantitatively analyzed. The negative thermal expansion material's thermal expansion was estimated with Raman peak shift.