Water-based polyurethane paint is widely used for wood furniture by virtue of the eco-friendliness, rich gloss, and flexible tailorability of its mechanical properties. However, its low solution (water or alcohol) resistance and poor hardness and wear resistance limit its application. The emerging graphene oxide has a high specific surface area and abundant functional groups with excellent mechanical properties, endowing it with great potential to modify waterborne polyurethane as a nanofiller. In this study, graphene oxide prepared by Hummers’ method is introduced in the chemosynthetic waterborne polyurethane through physical blending. The testing results demonstrate that the appropriate usage of graphene oxide at 0.1 wt% could obviously improve water absorption resistance and alcohol resistance, significantly enhancing the mechanical properties of waterborne polyurethane paint. The corresponding tensile strength, abrasion resistance, and pendulum hardness of the graphene oxide-modified paint film increase by 62.23%, 14.76%, and 12.7%, respectively, compared with the pristine paint film. Meanwhile, the composite paint film containing graphene oxide possesses superiority, including gloss, abrasion resistance, pendulum hardness, and tensile strength in contrast with the commercial paint. The use of graphene oxide to enhance the waterborne polyurethane possesses strong operability and practical value, and could provide useful reference for the modification of waterborne wood paint.