Graphene with high specific surface area was used to prepare water-ethanol-based suspensions for electrospinning, using PVP as processing aid as well as scaffold material. Different water/ethanol ratios as well as different polymer loadings were tested in order to adjust the rheological behavior and achieve stable spinning conditions. Continuous, defect-free fibers with embedded graphene were obtained after tuning the applied voltage, nozzle-collector distance and flow rate of suspension. Next, the graphene loading was progressively increased until defects in the form of graphene agglomerates appeared among the fibers. With the aid of a laser scanning microscope, graphene orientation along the fibers direction was detected above a critical loading value, due to the electric field and stretching of the polymer chains during electrospinning. In addition, graphene was replaced with a carbon byproduct from a gas reactor and similar results were obtained. Such fibers with embedded graphene may be used to provide reinforcement or to improve the thermal and electrical conductivities of refractories. In particular, a small amount of continuous fibers with embedded graphene may remarkably increase the mechanical and thermal properties of recycled carbon-bonded alumina refractories, which suffer from low thermal shock resistance due to the graphite flakes being broken down into very fine particles during the recycling process.