Here, we report the switching among multiple conductance pathways achieved by sliding the scanning tunneling microscope tip among different binding sites under different electric fields. With an increase in the electric field, high molecular conductance states appear, suggesting the formation of different configurations in single-molecule junctions. The switch can be operated in situ and reversibly, which is also confirmed by the apparent conductance conversion in I-V measurements. Theoretical simulations also agree well with the experimental results, which implies that the electric field enables the possibility to trigger switching in single-molecule junctions.