Toughening of boron carbide (B4C) without hardness degradation, was achieved by hierarchical structures consisting of B4C micro-grains, titanium diboride (TiB2) grains, and graphitic phases along B4C grain boundaries. Such hierarchical structures were uniquely achieved by co-sintering of B4C micro-powder and carbon-rich B4C nano-powder, in situ formation of TiB2, and by utilizing the short sintering time of field-assisted sintering technology. Toughening mechanisms observed after micro-indentation include crack deflection and delamination of graphite platelets, micro-crack toughening and crack deflection/bridging by TiB2 grains. Fracture toughness enhancement was achieved while maintaining hardness: 4.65 +/- 0.49 MPa m(1/2) fracture toughness and 31.88 +/- 1.85 GPa hardness for a micro/nano B4C-TiB2 composite (15 vol% TiB2 and 15 vol% B4C nano powders) vs. 2.98 +/- 0.24 MPa m(1/2) and 32.46 +/- 1.67 GPa for a reference micro B4C sample. In future, macro scale mechanical testing will be conducted to further evaluate how these micro-scale hierarchical structures can be translated to macro-scale mechanical properties.