The hydration of cement generates heat due to the exothermic nature of the hydration process. Poor heat dissipation in mass concrete results in a temperature gradient between the inner core and the outer surface of the element. High temperature gradients generate tensile stresses that may exceed the tensile strength of concrete thus leading to thermal cracking. The present paper is an attempt to understand the thermal (heat sink property) and microstructural changes in the hydrated graphene-Portland cement composites. Thermal diffusivity and electrical conductivity of the hydrated graphene-cement composite were measured at various graphene to cement ratios. The mass-volume method was implemented to measure the density of the hydrated graphene-cement composite. Particle size distribution of Portland cement was measured by using a laser scattering particle size analyzer. Heat of hydration of Portland cement was assessed by using a TAMAIR isothermal conduction calorimeter. Scanning electron microscopy (SEM) was implemented to study microstructural changes of the hydrated graphene-cement composites. The mineralogy of graphene-cement and the hydrated graphene-cement composites was investigated by using X-ray diffraction. The findings indicate that incorporation of graphene enhances the thermal properties of the hydrated cement indicating a potential for reduction in early age thermal cracking and durability improvement of the concrete structures.