Constructing various defects is considered to be a common viable means of improving electrochemical performance. However, it is of significance to thoroughly scrutinize the formation mechanism of defects and their effects and transition during the charge–discharge process. Here, twin structures are introduced into ZnSe0.7Te0.3 nanocrystals by doping of Te heteroatoms. The Te dopants are visualized to locate in the lattices of ZnSe by spherical aberration electron microscopy. The formation of twin structures is thermodynamically promoted by Te heteroatoms partially replacing Se based on the theoretical calculation results. Our findings show ZnSe0.7Te0.3 transforms into ZnSe and Te via the first cycling, which differ from the counterparts prepared by traditional methods and can effectively activate the interfacial and electronic effects due to the incomparable distribution and unmatched compatibility. It can be concluded that even though the initially constructed defects in materials of redox chemistry mechanism can’t resurrect, they play a critical role in tailoring the electrochemistry. We’re firmly convinced to pursue the exploitation of advanced and delicate electrode materials for batteries.