Five classes of spin-on dielectrics are discussed: polysilicates, polysiloxanes, polysilsesquioxanes, polyhydrocarbons, and polyimides. The emphasis is on the first three materials because very few polyhydrocarbon spin-on materials are available for study while spin-on polyimides sorb significant amounts of water. The polymer chemistry of the silicates, siloxanes, and silsesquioxanes is linkage through Si-O-Si-O bonds. Polyhydrocarbons are primarily linked through C-C bonds. As the name implies, polyimides are linked through (usually aromatic) imide groups. Because of their polar nature, polyimides, polysilicates, and polysiloxanes have dielectric constants >3, while the large hydrocarbon content of the remaining materials results in a dielectric constant of <3. Films of polysilicates are relatively brittle and thus are limited to a thickness <1 μm. On the other hand, films of polysilsesquioxanes, polyimides, and polyhydrocarbons can be readily deposited to a thickness >1 μm. Polysilicates have high temperature (>900°C) stability and do not react with O2; most polyhydrocarbons decompose above ˜350°C and oxidize readily; some polyimides are stable to 500°C; polysiloxanes and polysilsesquioxanes readily survive 425°C in N2. (Films of the latter two materials are converted to silicates upon heating at high temperatures in O2 or steam.) The infrared spectrum of a 425°C-cured silicate film shows the presense of Si-OH bonds and water, but after a 900°C anneal, the spectrum is almost identical to that of thermal oxide. The spectra of films of polysiloxanes or polysilsesquioxanes do not exhibit Si-OH absorption. Water retention in films is deleterious to the electrical and mechanical (swelling) properties of the dielectric and to making good aluminum-to-aluminum electrical contact through submicron vias. The water leads to a mobile charge (H+) phenomenon that is readily detected by a Triangular Voltage Sweep technique. Except for polysilicates, solutions of the other spin-on materials have reasonably long (weeks-to-months) shelf-lives. Polysilicate solutions are sols and tend to gel; the time to gelling is a function of solids content and solvent. Even though they exhibit shortcomings, polysiloxanes appear to be best suited as interlevel dielectrics in multilevel metalization schemes.