A facile route to graphene/polymer hydrogel nanofibers was developed. An aqueous dispersion of graphene (containing >40% bilayer graphene flakes) stabilized by a functionalized water-soluble polymer with phenyl side chains was successfully electrospun to yield nanofibers. Subsequent vapor-phase cross-linking of the nanofibers produced graphene-embedded hydrogel nanofibers (GHNFs). Interestingly, the GHNFs showed chemical sensitivity to the cationic dyes methylene blue (MB) and crystal-violet (CV) in the aqueous phase. The adsorption capacities were as high as 0.43 and 0.33 mmol g(-1) s(-1) for MB and CV, respectively, even in a 1.5 mL s-1 flow system. A density functional theory calculation revealed that aqueous phase MB and CV dyes were oriented parallel to the graphene surface and that the graphene/dye ensembles were stabilized by secondary physical bonding mechanisms such as the pi-pi stacking interaction in an aqueous medium. The GHNFs exhibited electrochemical properties arising mainly from the electric double-layer capacitance, which were applied in a demonstration of GHNF-based membrane electrodes (5 cm in diameter) for detecting the dyes in the flow system. It is believed that the GHNF membrane can be a successful model candidate for commercialization of graphene due to its easy-to-fabricate process and remarkable properties.