Anisotropic orientation of carbon fiber (CF)/liquid crystalline epoxy (LCE) resin composite was readily induced during curing on a CF surface along a long molecular axis of CF Orientation of LCE was confirmed with polarized optical microscope (POM) and wide angle X-ray diffractometer (WAXD). In addition, anisotropic ordering of LCE was correlated with curing rate, dynamic mechanical properties and thermal expansion behaviors of CF/LCE composite. Curing of LCE was accelerated in the presence of CF and the rubbery modulus of the CF/LCE composites cured at low temperature was enhanced by long-range, long axis orientational ordering of the LCE resin along a CF surface. Fully cured CF/LCE composite showed a negative coefficient of thermal expansion in the fiber direction. These results obtained in this study are interpreted in terms of structural changes occurring during curing.