Chemical modification of hardwood sawdust from ash-tree species was carried out with a solution of maleic anhydride in acetone. Wood polymers, lignin, and cellulose were isolated from the wood sawdust and modified by the same method. Samples were characterized by Fourier transform infrared spectroscopy (FTIR), providing evidence that maleic anhydride esterifies the free hydroxyl groups of the wood polymer components. Composites comprising chemically modified wood sawdust and wood polymers (cellulose, lignin)-as variable weight percentages-, and poly (vinyl chloride) were obtained and further characterized by using FTIR spectroscopy and scanning electron microscopy (SEM). The thermal behavior of composites was investigated by using the thermogravimetric analysis (TGA). In all cases, thermal properties were affected by fillers addition.