Abstract Recently, off-centering behavior has been discovered in a series of thermoelectric materials. This behavior indicates that the constituent atoms of the lattice displace from their coordination centers, leading to the locally distorted state and local symmetry breaking, while the material still retains its original crystallographic symmetry. This effect has been proved to be the root cause of ultralow thermal conductivity in off-centering materials, and is considered as an effective tool to regulate the thermal conductivity and improve the thermoelectric performance. Herein, we present a collection of recently discovered off-centering compounds, discuss their electronic origins and local coordination structures, and illuminate the underlying mechanism of the off-centering effect on phonon transport and thermal conductivity. This paper presents a comprehensive view of our current understanding to the off-centering effect, and provides a new idea for designing high performance thermoelectrics.