Mercury (Hg) emitted from coal-based thermal power plants (CTPPs) can accumulate and bio-magnify in the food chain, thereby posing a risk to humans and wildlife. The central idea of this study was to develop an adsorbent which can concurrently remove elemental mercury (Hg) and SO emitted from coal-based thermal power plants (CTPPs) in a single unit operation. Specifically, a composite adsorbent of CaCO impregnated with 2-mercaptobenimidazole (2-MBI) (referred to as modified calcium carbonate (MCC)) was developed. While 2-MBI having sulfur functional group could selectively adsorb Hg, CaCO could remove SO. Performance of the adsorbent was evaluated in terms of (i) removal (%) of Hg and SO, (ii) adsorption mechanism, (iii) adsorption kinetics, and (iv) leaching potential of mercury from spent adsorbent. The adsorption studies were performed using a 2 full factorial design of experiments with 15 ppbV of Hg and 600 ppmV of SO. Two factors, (i) reaction temperature (80 and 120 °C; temperature range in flue gas) and (ii) mass of 2-MBI (10 and 15 wt%), were investigated for the removal of Hg and SO (as %). The maximum Hg and SO removal was 86 and 93%, respectively. The results of XPS characterization showed that chemisorption is the predominant mechanism of Hg and SO adsorption on MCC. The Hg adsorption on MCC followed Elovich kinetic model which is also indicative of chemisorption on heterogeneous surface. The toxicity characteristic leaching procedure (TCLP) and synthetic precipitation leaching procedure (SPLP) leached mercury from the spent adsorbent were within the acceptable levels defined in these tests. The engineering significance of this study is that the 2-MBI-modified CaCO-based adsorbent has potential for concurrent removal of Hg and SO in a single unit operation. With only minor process modifications, the newly developed adsorbent can replace CaCO in the flue-gas desulfurization (FGD) system.