The figure represents an increase of 0.2 percentage point from the previous quarter, and marks the highest level since the July-September period of 2010, the Bank of Korea (BOK) said.
The use of the greenback for export settlements increased for four consecutive quarters.
Kim Min-woo, chief of the BOK's balance of payments team, attributed the rise to a hike in South Korean exports to the United States as the U.S. economy is on a recovery track.
According to him, shipments to the United States soared 22.2 percent in the last quarter from the same period of 2013.
The International Monetary Fund (IMF) revised up the U.S. economic growth for 2015 to 3.6 percent from an earlier estimate of 3.1 percent, citing more robust private domestic demand.
Meanwhile, the portion of Japanese yen in export settlement accounted for an all-time low of 3.0 percent of the total in the last quarter, down 0.1 percentage point from three months earlier, an indication that exports to Japan declined due to a prolonged weakness of the yen, the BOK said.
The comparable figure stood at 5.3 percent for euro, up from 5.1 percent three months earlier; and 2.2 percent for Korean won, down from 2.3 percent.