Cross-linking starch microsphere (CSM) is a derivative of crude starch and has been studied and applied widely in the fields of medicine and sanitary devices. In our studies we have found that starch microsphere has good adsorption performance to metal ions in water. In this work, a type of cross-linking starch microsphere has been synthesized by reversed phase suspension method using soluble starch as raw material with N,N'-methylenebisacrylamide as a cross-linking agent. The observation through scanning electron microscopy (SEM) shows that CSM is a homogeneous mixture of spherical particulates with heterogeneous surface with particles' average diameter of about 50 mm. The structure characteristics of carbonyl group and second acylamide in Fourier transform infrared spectroscopy spectrogram of CSM demonstrates that the soluble starch is definitely cross-linked with N,N'-methylenebisacrylamide. The synthetic analysis of X-ray diffraction indicates that the cross-linking function decreases the crystallinity of CSM compared with that of soluble starch. The adsorption capacity of CSM towards Cu2+, Co2+, and Ni2+ increases with the increase in metal ion concentration, and by lowering the temperature, adsorption can be accelerated. The adsorption behaviour of CSM in different temperatures is in agreement with the Freundlich isothermal equation. The research results show that the adsorption process is exothermic, can proceed spontaneously, with the adsorption force mainly derived from enthalpy changes. The thermodynamic parameters of adsorption process show that the adsorption behaviour of CSM towards Cu2+, Co2+, and Ni2+ is of a physical type.