AbstractRice hulls, a byproduct of the rice industry, contain 60–90% silica and are unique within nature. The annual worldwide output of rice‐hull‐derived silica is more than 3.2 million tons, which poses environmental concerns because of disposal issues. Burning rice hulls, as a preparative step for energy production, is a useful solution to the growing environmental concern, a desirable outcome would be the economic use of the resulting silica‐rich hull ash. The economical usefulness of this silica ash in the filler market has been undermined by its limited dispersion abilities and poor interaction capability with polymers. In this study, some of the reasons for the poor performance of silica ash as a reinforcing filler in various polymeric composites were linked to its inherent characteristics: factors such as its impurity, irregular topography, porosity, and chemical and thermodynamic nature arising from its surface polarity that negatively influence the filler–matrix interactions. The silica ash obtained from a novel combustion process had about 6% (w/w) impurity, of which around 3% was volatile. We also propose that the silanation efficiency of silica ash is lower compared to other commercial silicas because of its porosity, which could hide a fraction of the silane used. Also, processing changed the particle size distribution, and this could have affected the agglomerating tendencies and seriously marked the reinforcing capabilities of the silica ash. The estimation of the surface silanol groups of the rice hull ash by thermogravimetric studies indicated that the surface silanol density was about 16/nm2. On a comparative scale, this value is comparable to the silanol density on precipitated silica, but a thermodynamic study of silica ash surface revealed a high surface free energy that contributed to its high aggregation tendencies and poor distribution and dispersion abilities. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1–8, 2004