A series of novel superabsorbent composites of poly(acrylic acid)/semicoke were prepared by polymerization of acrylic acid using ammonium persulphate as initiator, N,N′-methylenebisacrylamide as crosslinker and semicoke which was the by-product of coal carbonizing as the inorganic components. FTIR and SEM analysis indicated that the superabsorbent composites had been successfully polymerized and the semicoke participated in construction of the 3D polymeric network. Meanwhile, the effects of initiator, crosslinker, semicoke, and neutralization degree, as well as the pH value, were investigated, and the results showed that superabsorbent composites containing 10% of semicoke possessed the maximum water absorbency of 584 g/g in distilled water and 75 g/g in 0.9% NaCl solution. The superabsorbent composites kept the high water absorbency within a wide pH range of 4–11, and still exhibited better re-swelling capability even after seven times. The superabsorbent composite with its excellent performance is a potential water-retaining agent used in agriculture.