Two chemical treatments were applied to hemp, sisal, jute and kapok natural fibres to create better fibre to resin bonding in natural composite materials. The natural fibres have been treated with varying concentrations of caustic soda with the objective of removing surface impurities and developing fine structure modifications in the process of alkalisation. The same fibres were also acetylated with and without an acid catalyst to graft acetyl groups onto the cellulose structure, in order to reduce the hydrophilic tendency of the fibres and enhance weather resistance. Four characterisation techniques, namely XRD, DSC, FT-IR and SEM, were used to elucidate the effect of the chemical treatment on the fibres. After treatment the surface topography of hemp, sisal and jute fibres is clean and rough. The surface of kapok fibres is apparently not affected by the chemical treatments. X-ray diffraction shows a slight initial improvement in the crystallinity index of the fibres at low sodium hydroxide concentration. However, high caustic soda concentrations lower the fibre crystallinity index. Thermal analysis of the fibres also indicates reductions in crystallinity index with increased caustic soda concentrations and that grafting of the acetyl groups is optimised at elevated temperatures. Alkalisation and acetylation have successfully modified the structure of natural fibres and these modifications will most likely improved the performance of natural fibre composites by promoting better fibre to resin bonding.