With unique 2D nanostructures and excellent properties, graphene and its derivatives are a class of advanced nanosized reinforcements for cementitious materials. Sulfonated graphene (SG), one of the most important modified graphene materials, possesses sulfonate groups on the surface and significantly improves the mechanical and thermal properties of cement-based composites. It is important to investigate the influence of SG on cement-based materials as it is a prerequisite for practical applications. Herein, SG was prepared and introduced into cement paste to investigate its influence on the rheological properties of cement paste. With the increased addition of SG, a stable slurry was gradually obtained with low fluidity and high rheological parameters. The mechanism of the SG effect on the rheological properties of cement paste was also illustrated. Because of the high specific surface area and sulfonate groups of SG nanosheets, a large amount of flocculated structure was created by the complexing effect, chemical interaction, physical interaction and mechanical interlocking between SG and hydrated/unhydrated cement particles. Furthermore, polycarboxylate ether (PCE) superplasticizer was introduced to ensure fluidity and transportability in the practical application of SG. The results in this work lay a foundation for the practical application of modified graphene in cementitious materials.