A study of the manufacturing and characterisation of poly (vinyl alcohol) (PVA) nanofibre mats reinforced with microcrystalline cellulose (MCC) is presented. Results obtained from Attenuated Total Reflection Fourier Transform Infrared (ATR-FTIR) spectrometry and Scanning Electron Microscopy (SEM) of the products are discussed and interpreted. PVA nano-fibre mats reinforced with MCC nano-whiskers (CNWs) were prepared from aqueous PVA solutions by NanospiderTM high-voltage electro-spinning on NS Lab 200 (Elmarco) equipment with a circular cylinder as the emitting electrode. PVA/CNWs mats of a modal nano-fibre diameter of 300 nm and average diameter within the range from 350 to 294 nm were obtained by the electro-spinning technique. Solution parameters, such as the content of CNWs in the solution and PVA concentration and viscosity were varied in an attempt to produce possibly finer cellulose nano-fibres.