There are provided processes and compositions for obtaining organic polymeric materials having near-zero uniaxial thermal expansion coefficients. According to one embodiment, an organic polymer having a negative uniaxial thermal expansion coefficient is treated by thermal processing under conditions sufficient to cause at least a portion of the polymer chains to become misaligned, thereby decreasing the magnitude of this thermal expansion coefficient to nearly zero. According to a second embodiment, one or more organic polymers having a negative uniaxial thermal expansion coefficient are combined with one or more materials having a positive thermal expansion coefficient to yield a composite material having a uniaxial thermal expansion coefficient which is nearly zero.Useful in the practice of the invention are polyacetylenes having a negative macroscopic thermal expansion coefficient, which are obtained by the solid-state polymerization of crystalline monomers containing two or more conjugated acetylene groups.