Achieving a uniform dispersion of reduced graphene oxide (RGO) nanosheets in waterborne polymer matrix remains a challenge. Here, we significantly improved the dispersion stability of RGO in a polymer matrix through functionalizing RGO with titanate coupling agent of different dendritic structure. Titanate coupling agents of two branched dioctylpyrophosphate (T2) and three branched dioctylpyrophosphate (T3) were used. Rather than simply blending graphene with polymer matrix, functionalized graphene (T2-RGO or T3-RGO) was introduced into the reaction system with monomers to participate in the polymerization; resulting in improved compatibility and interaction between the graphene and polymer, especially for T3-RGO. One-component waterborne poly (urethane-acrylate) nanocomposite coatings (WPUA/T2G or WPUA/T3G) were then obtained. The particle size of WPUA/T3G colloidal particle size is much smaller than that of WPUA/T2G, the colloidal stability was also increased with the incorporation of T3-RGO. Compared with pure WPUA, the tensile strength of WPUA/T3G nanocomposite increased from 17.78 MPa to 40.01 MPa, and the elongation at break increased from 249% to 424%. The tensile strength and elongation at break of WPUA/T2G were 32.01 MPa and 366%, which were inferior to that of WPUA/T3G. Moreover, in comparison with pure WPUA, the impedance modulus of WPUA/T3G increased from 1.12 × 105 Ω.cm2 to 1.15 × 108 Ω.cm2, the coating resistance of WPUA/T3G increased from 8.41 × 104 Ω.cm2 to 1.39 × 108 Ω.cm2, which was also much higher than the impedance modulus (6.93 × 106 Ω.cm2) and coating resistance (7.31 × 106 Ω.cm2) of WPUA/T2G. WPUA/T3G nanocomposite coating exhibited excellent long-term corrosion resistance, being superior to the previously reported performance of solventborne polyurethane/graphene composite.