Advances in nanofibre application, such as water treatment, have increased the need to identify renewable resources and green methods for nanofibre production. In this study, natural rubber latex (NRL) mixed with polyvinyl alcohol (PVA) was electrospun to form nanofibre films, and the best PVA/NRL ratio suitable for aqueous applications was determined. The films were characterised by scanning electron microscopy (SEM), Fourier-transform infrared (FT-IR) spectroscopy and a weight loss test by dissolution. SEM images revealed relatively thicker and smoother fibres, with larger average pore diameters in fibre films with higher PVA content (60% PVA/NRL and 70% PVA/NRL). Fibre films with lower PVA content (40% PVA/NRL and 50% PVA/NRL) had relatively thinner fibres and smaller average pore diameters, which are desirable characteristics for contaminant adsorption. The FT-IR spectroscopy indicated that 60% PVA/NRL and 70% PVA/NRL would be more soluble in water than 40% PVA/NRL and 50% PVA/NRL due to the intense peaks of C = O stretching of acetate groups (1738 cm−1) observed in fibre films with higher PVA content. This was confirmed in a weight loss test, which revealed that though increasing PVA content (60 and 70%) improved NRL’s electrospinnability, the increased PVA content caused a loss of fibre film mass in water. Therefore, 50% PVA/NRL will be a better option for application in aqueous processes.