Exploratory synthetic adventures regarding the inorganic chemistry of polar intermetallic phases have proven to be especially productive of novel compositions, new and unprecedented structures, and unusual bonding regimes. Reactions of diverse elements with widely different electronegativities allow the definition of two opposed classes of products: polycationic or polyanionic clusters or networks of metals paired with the corresponding monatomic anions or cations. These can be usefully viewed as intermetallic "salts", redox products of simpler neutral intermetallic systems but with widely different factors governing their stabilities. Thus, combinations of rare-earth metals alone or with late transition metals form a novel variety of polymetal network structures with relatively isolated telluride (or halide) spacer anions. Similarly, extensions of traditional Zintl phases of the alkali or alkaline-earth metals from the later p elements to the earlier triels, Ga-Tl especially, yield many new and elegant polyanionic structures. The substitution or addition of still earlier p or late d metal components produces still electron-poorer and more condensed polar intermetallic phases with increasingly delocalized bonding, higher coordination numbers, and more unusual structures and bonding. These discoveries have also led to new approaches: electronic tuning via band calculations to generate new families of quasicrystals and their crystalline approximants with their characteristic structural regimes and regularities. Gold as a substituent generates particularly novel bonding in arrays of mixed metals or polygold anionic networks.