Using natural gas as carbon source, 2D needle felt as preform, 2D-C/C composites were prepared by thermal gradient chemical vapor infiltration. Their microstructures were observed under polarized light microscope (PLM) and scanning electron microscope (SEM), and the flexural behaviors before and after heat-treatment were studied with a universal mechanical testing machine. The fracture mechanism of the composites was discussed in detail. The results show that, carbon matrix exhibits pure smooth laminar (SL) characteristic including numerous wrinkled layered structures and some inter-laminar micro-cracks. With the decreasing density, the strength of the composites decreases and the toughness increases slightly; after 2500 °C heat-treatment, the inter-laminar micro-cracks in matrix increase, the strength decreases, and the toughness obviously increases. The fracture mode of the composites changes from brittle to pseudo-plastic characteristic due to more crack deflections in SL matrix.