Polymeric gel composed of high hydrolyzed grade poly(vinyl alcohol) and surface-modified waste fly ash has been synthesized and reported for the first time. Organic chlorosilane has been used as the surface modifier for the as-received fly ash samples for strong interaction with poly(vinyl alcohol). The resultant gels are visually transparent and thermally stable as compared to the virgin poly(vinyl alcohol). These are also mechanically stronger than the base polymer and as-received fly ash/poly(vinyl alcohol) gels due to better polymer-surface-modified fly ash interaction as reflected from their viscometric results. © 2010 The Author(s).