Interface failure due to thermal mismatch is one of the culprits that shorten life cycle of devices. In this work, we prepared a series of free-standing cross-linked polyarylamide films with tunable thermal responsive behaviors. By incorporating thermal contractile units, s-dibenzocyclooctadiene (DBCOD), which shrink as a result of thermally induced upconversion from twist boat to chair, negative, zero, and positive coefficients of thermal expansion (CTE) have been realized with the values of CTE ranging from -17.7 to 57.1 ppm/K (20-150 degrees C). This wide tunable CTE window allows the as-prepared cross-linked polyarylamide films to match desired thermal performance for specific applications. Zero-expansion polymer film without the need for inorganic dopants has also been obtained. Such a series of free-standing polyarylamide films with tunable thermal responses showed great potential for many practical applications.