The strong adsorbability of Ag(I) ions onto poly(3-mercaptopropylsilsesquioxane) (PMPSQ) microspheres synthesized through a two-step acid–base catalyzed sol–gel process method was systematically examined. The effect of adsorption time, initial Ag(I) concentration, and solution pH was studied to optimize the Ag(I) adsorbability of PMPSQ microspheres. The PMPSQ microspheres demonstrate a powerful Ag(I) adsorbability with an adsorptivity above 99.99% when the initial Ag(I) concentration is lower than 10mM and the highest Ag(I) adsorbance of 1140mg/g at an initial Ag(I) concentration of 150mM. Adsorption phenomena appeared to follow Langmuir isotherm. The kinetic studies indicated that the adsorption process well fits the pseudo-second-order kinetics with a very rapid initial adsorption rate of 15.28mgg −1 min −1 . The appropriate solution pH for Ag(I) adsorption is around 2.0–5.4. The PMPSQ microspheres demonstrate a promising application in the removal of Ag(I) ions from aqueous solutions.