The original number of the road west of Rotherham through Chapeltown to meet the A629 at Charltonbrook was A632.
Starting on the A630 Effingham Street in Rotherham town centre, the road headed west, crossing the River Don on Rotherham Bridge (where there is still a bridge chapel) and then the railway line at Masbrough station. After climbing steadily for a couple of miles the road then descended along a steep, winding road into Chapeltown where it crossed the A61 (now A6135). It then climbed again through Charltonbrook to end on the A629 (now A61).
In 1935, the A61 was rerouted along the A629 north of Sheffield; in return the A629 was rerouted along the entire length of the A632 so that it ended in Rotherham instead of Sheffield, freeing the A632 number for use in the Chesterfield area. Owing to a weight restriction, the section of former A632 between the old and current routes of the A61 is now numbered B6546.