Charged domain walls (CDWs) are of significant scientific and technological importance as they have been shown to play a critical role in controlling the switching mechanism and electric, photoelectric, and piezoelectric properties of ferroelectric materials. The atomic scale structure and properties of CDWs, which are critical for understanding the emergent properties, have, however, been rarely explored. In this work, using a spherical-aberration-corrected transmission electron microscope with subangstrom resolution, we have found that the polarization bound charge of the CDW in rhombohedral-like BiFeO3 thin films not only induces the formation of a tetragonal-like crystal structure at the CDW but also stabilizes unexpected nanosized domains with new polarization states and unconventional domain walls. These findings provide new insights on the effects of bound charge on ferroelectric domain structures and are critical for understanding the electrical switching in ferroelectric thin films as well as in memory devices.