The agglomeration of reduced graphene oxide (rGO) in water makes the development of rGO inks for supercapacitor printing challenging. Cellulose nanofiber (CNF), a biodegradable and renewable nanomaterial, can act as a nanospacer, preventing the agglomeration and restacking of rGO flakes. In this work, rGO/CNF films were fabricated using an environmentally friendly water-based rGO/CNF ink. In the absence of an additional binder/surfactant, the rGO/CNF films demonstrated remarkably enhanced hydrophilicity while retaining good electrical conductivity. The concentration of CNF was varied to observe the variation in the electrochemical performance. At a current density of 1 mA/cm2, the rGO/CNF-15 film exhibited a maximum areal capacitance of 98.61 mF/cm2, closely matching that of pure rGO films. Because of its excellent electrical performance, ease of manufacturing, and environmental friendliness, this water-based rGO/CNF ink may have promising applications in the printing of supercapacitor electrodes.