Even after ca. four decades of R&D effort, we still do not have a "magic bullet" inorganic semiconductor to photoelectrochemically generate fuels or chemicals from sunlight in a sustainable, efficient and environment-friendly manner. While it is unlikely that a single semiconductor candidate will emerge that simultaneously satisfies all the optical, electrical, surface chemical, and electrochemical prerequisites for efficient solar conversion, complex oxides or chalcogenides (or derivatives thereof, e.g., oxynitrides) do provide a versatile framework for rational design of the "perfect beast" in a chemical architectural sense. Ultimately two or more such semiconductor compositions can be combined in a composite design much like complementary functionalities are combined in photosynthetic assemblies in Nature. In such designs, the semiconductor(s) and the photoactive junction can even be separated from the electrolyte and the electrocatalyst component in a "buried junction" design. In this vein, the author's laboratory has been engaged in the development of time- and energy-efficient methods for synthesizing new families of photoelectrode or photocatalyst materials. In this particular talk, the author will provide first a context for the key role that solid-state chemistry paradigms and principles can play in photoelectrode designs for driving multi-electron processes typical of solar fuel generation. Two representative ternary semiconductor systems, namely, Cu-V-O and M-Ln-X (M = divalent metal, e.g., Ba, Ln = lanthanide element, e.g., Ce, and X = chalcogen, e.g., S) will be discussed in this talk.