The fly ash with a loose and porous structure has definite absorbent ability, which has a good effect on soil improvement. Illite belongs to clay minerals, it has absorbent ability and higher potassium, which can improve the soil fertility. In this study, poly(acrylic acid sodium-co-acrylamide)(PAANa-AM)/fly ash-illite superabsorbent composite was firstly prepared by solution polymerization. The structures were characterized using scanning electron microscope, X-ray diffraction, and infrared spectrum. The results showed that the fly ash and illite dispersed well in the composite. The K+ in illite was replaced by Na+ in acrylic acid sodium and thus the illite structure turned into paragonite during the process of preparing composite, however, the structure of fly ash was maintained in the composite. Moreover, the hydroxide radical in illite reacted with the carbonyl group in acrylic acid during polymerization. The best absorbent capacities of the composite in distilled water, tap water and normal saline were 1695, 445 and 106 g/g, respectively, which exceeded the requirements of The National 863 Program and Ministry of Agriculture of People’s Republic of China. The potassium release was measured using atomic absorption spectrometry and the results indicated that the composite can release 12.80% of the potassium ion in fly ash and illite. The superabsorbent material has low cost and favors improvement of soil and potassium-deficiency.