Controlled-ionic-composition waterflooding is an economic and effective method to improve oil recovery in carbonate oil reservoirs. Recent studies show controlling the salinity and ionic composition of injection water can alter the wettability of carbonate mineral surfaces. The pore-scale oil connectivity and displacement by controlled-ionic-composition waterflooding in heterogeneous carbonate reservoirs, especially at the early stage, is still unclear. The goal of this study is to examine the role of ion concentrations and types in the oil displacement efficiency and investigate the impact of the waterflooding on the pore-scale oil displacement using the national synchrotron facility. A carbonate rock sample was flooded with synthetic high-salinity water and other water solutions with different sulfate concentrations. The waterflooding processes were visualized with synchrotron X-ray microtomography to follow the evolution of pore-scale oil/brine interactions at typical field flow rates. Experimental results show that the water with lower sulfate concentration and higher salinity did not change the wettability of the pore surfaces. Higher sulfate ion concentrations in the water, in contrast, altered the wettability of carbonate pore surfaces from oil-wet to neutral-wet within the first few minutes of waterflooding. Novel insight was gained on the ability of water with high-sulfate concentration to displace oil in the small pores and through abundant oil channels, which could consequently lead to higher oil recovery from the carbonate rock.