Electrospun zein-polyvinylpyrrolidone (PVP) ultrafine fibres containing varying polymer ratios were prepared and characterised. Ketoprofen was used as a model drug incorporated into the polymer system. The fibre morphologies, the composite physical states and their interactions were investigated using scanning electron microscopy (SEM), differential scanning calorimetry (DSC), X-ray diffraction (XRD), and Fourier transform infrared (FTIR) spectroscopy. Scanning electron microscopy observations revealed that ketoprofen was well distributed in the polymer matrix. Both the surface and cross-sections of fibres were homogeneous, although they characteristically became rounder as the content of PVP in the composite increased. Results from FTIR, DSC and XRD suggested that ketoprofen exist as an amorphous solid dispersion state in the matrix. The influence of zein-to-PVP content on the drug release profiles was investigated using in vitro dissolution tests under controlled conditions. The results prove that ketoprofen release rates increased at a higher PVP level. The present research demonstrates that zein can be introduced into a fibre composite that effectively has the potential to act as matrix for drug release. This is the first report of zein acting in this context.