Relaxor ferroelectric perovskites are highly polarizable and can exhibit giant coupling between elastic strain and an applied electric field. Here, we report an in situ extended X-ray absorption fine structure (EXAFS) study of a PbZn1/3Nb2/3O3 (PZN) single crystal as a function of the electric field. We show that the strong dipoles in the NbO6 octahedra bonds are aligned along the four ⟨011⟩ directions close to the orientation of the electric field, while a small reversible polar shift occurs for Zn in the direction of the electric field, i.e., positive or negative. This reversible Zn-O polar shift is proposed to play an important role in both the "easy" switching of the ferroelectric polarization and the giant piezoelectric effect in PZN.