This study develops a novel self-sensing cement composite by simply mixing reduced graphene oxide (rGO) in cementitious material. The experimental results indicate that, owing to the excellent dispersion method, the nucleation and two-dimensional morphological effect of rGO optimizes the microstructure inside cement-based material. This would increase the electric conductivity, thermal property and self-induction system of cement material, making it much easier for cementitious material to better warn about impending damage. The use of rGO can improve the electric conductivity and electric shielding property of rGO-paste by 23% and 45%. The remarkable enhancement was that the voltage change rate of 1.00 wt.%-rGO paste under six-cycle loads increased from 4% to 12.6%, with strain sensitivity up to 363.10, without compromising the mechanical properties. The maximum compressive strength of the rGO-mortar can be increased from 55 MPa to 71 MPa. In conclusion, the research findings provide an effective strategy to functionalize cement materials by mixing rGO and to achieve the stronger electric shielding property and higher-pressure sensitivity of rGO–cement composites, leading to the development of a novel high strength self-sensing cement material with a flexural strength up to 49%.