We explore some aspects of the optimization of amorphous semiconductors as well as low- and high-dielectric-constant (low-/high-k) materials viewed purely from the perspective of percolation and topological constraint theories. We specifically illustrate how percolation, constraint theory, and mean network coordination, 〈r〉, play underlying roles in determining the electrical and mechanical properties of amorphous semiconducting and dielectric materials as well as interfaces that are important for modern micro-/nanoelectronic devices.