Ordering of charge/spin/orbital degrees of freedom in complex materials accompanies domains and domain walls associated with the directional variants (Zm) and also antiphases (Zn). It has been recently realized that nontrivial ZmxZn topology can exists in large-scale real-space configurations of domains and domains walls of complex materials. Furthermore, the vertices where domain walls merge can be considered as topological defects with well-defined vorticities (Zl vortices). I will present the recently-discovered examples of ZmxZn domains and Zl vortices in complex materials. We will also discuss emergent physical properties of domain walls, which are distinctly different from those of domains.