With the aim of achieving controllable mass production of electrospun nanofiber films, this study proposes and investigates the feasibility of using a custom-made linear electrode- electrospun device to produce conductive graphene (GR)-filled polyvinyl alcohol (PVA) nanofibers. The film morphology and diameter of nanofibers are observed and measured to examine the effects of viscosity and conductivity of the PVA/GR mixtures. Likewise, the influence of the content of graphene on the hydrophilicity, electrical conductivity, electromagnetic interference shielding effectiveness (EMSE), and thermal stability of the PVA/GR nanofiber films is investigated. The test results show that the PVA/GR mixture has greater viscosity and electric conductivity than pure PVA solution and can be electrospun into PVA/GR nanofiber films that have good morphology and diameter distribution. The diameter of the nanofibers is 100 nm and the yield is 2.24 g/h, suggesting that the process qualifies for use in large-scale production. Increasing the content of graphene yields finer nanofibers, a smaller surface contact angle, and higher hydrophilicity of the nanofiber films. The presence of graphene is proven to improve the thermal stability and strengthens the EMSE by 20 dB at 150–1500 MHz. Mass production is proven to be feasible by the test results showing that PVA/GR nanofiber films can be used in the medical hygiene field.