Dried, milled perennial ryegrass samples were processed using chemical and physical treatments and the extracted cellulose products were analysed for yield, crystallinity by X-ray Diffraction (XRD) and for purity using Thermogravimetric Analysis (TGA), Pyrolysis-Gas Chromatography/Mass Spectrometry (Py-GC/MS) and Fourier Transform Infrared (FTIR) spectroscopy. Extraction protocols examined the use of chemical chelation, acid and alkaline hydrolysis, along with physical degradation methods. Highest product yields were obtained using single step chemical protocols followed by physical processing, however, these products had low crystallinity and higher amorphous fraction content. Multistep chemical processing to completely remove hemicellulose and lignin with an alkali refluxing step, delivered lower yielding cellulose products of greater crystallinity and purity. In combination, the four instrumental techniques highlighted removal of amorphous fractions, providing rapid, accurate compositional data on the extracted cellulose products. Crown Copyright (c) 2013 Published by Elsevier Ltd. All rights reserved.