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The thermal conversion of rice straw is an attractive option for recovering its energy, but the process requires exhaustive control because of ash-related problems. Straw washing is one method of reducing ash-related problems and improving combustion behaviour. In this study, the ash of washed and unwashed rice straw samples was chemically characterized, tested using thermogravimetric analysis and environmental scanning electron microscopy (ESEM), and subjected to higher combustion temperatures in a muffle furnace. Results showed that silicon was the most important component in the ash. Furthermore, a reduction in undesirable inorganic compounds related to ash problems, such as chlorine and potassium, was achieved by washing the straw samples. This practice could improve thermal behaviour and decrease the sintering formation of ash.