This paper is concerned with an analysis of the electrical conductivity of graphene/cement composites by means of DC (direct current) and AC (alternating current) techniques. Moreover, the micrograph and element composition of composites have been characterized through SEM (scanning electron microscopy) and EDS (energy-dispersive spectrometers) techniques, respectively. Results revealed that a percolation transition region Φ2-Φ1 (Φ2 and Φ1 values are determined as 0.8% and 1.8%, respectively) can be observed in the S-shaped curve. In addition, the logistic model has been recommended to characterize the relationship between the conductivity and the graphene concentration, which ranged from 0.001% to 2.5%. The micrographs obtained by SEM technique clearly indicate a complete conductive network as well as agglomeration of graphene slices when the graphene content reaches the threshold value. Furthermore, graphene slices can be distinguished from the cement hydration products by means of the analysis of element composition obtained through the EDS technique. It is promising to apply the graphene/cement composites as intelligent materials.