In contrast to the flexible rotation of magnetization direction in ferromagnets, the spontaneous polarization in ferroelectric materials is highly confined along the symmetry-allowed directions. Accordingly, chirality at ferroelectric domain walls was treated only at the theoretical level and its real appearance is still a mystery. Here we report a Neel-like domain wall imaged by atom-resolved transmission electron microscopy in Ti-rich ferroelectric Pb(Zr1-xTix) O-3 crystals, where nanometre-scale monoclinic order coexists with the tetragonal order. The formation of such domain walls is interpreted in the light of polarization discontinuity and clamping effects at phase boundaries between the nesting domains. Phase-field simulation confirms that the coexistence of both phases as encountered near the morphotropic phase boundary promotes the polarization to rotate in a continuous manner. Our results provide a further insight into the complex domain configuration in ferroelectrics, and establish a foundation towards exploring chiral domain walls in ferroelectrics.