Electrospinning technology for fabricating nanofiber films and the Hummer method for synthesizing graphene oxide (GO), along with subsequent reduction, have been significantly advanced, demonstrating immense potential for large-scale industrial applications. Nanofibrous films loaded with reduced graphene oxide (rGO) have been widely explored for their applications in electromagnetic shielding, the biomedical fields, and pollutant adsorption. However, fragile mechanical performance of electrospun fibers with limited surface post-treatment methods has somewhat hindered their further industrial development. In response to this challenge, we propose a dual-regulation strategy involving post-treatment to form porous nanofiber films and the controlled flake size of rGO for surface coating during preparation. This approach aims to achieve poly(l-lactic acid) (PLLA)/rGO electrospun fibrous films with enhanced mechanical properties. It offers a roadmap for the continued application and standardized production of fibrous films loaded with rGO.