A topologically unique, conformationally constrained tetradentate ligand system for polymetallic coordination chemistry has been developed: tetrakis(2-hydroxyphenyl)ethene (1a) and substituted derivatives. The design exploits the planarity of the tetraphenylethylene core to impart rigidity to the roughly square oxygen binding array, while maintaining a degree of conformational mobility associated with rotation about the aryl-ethylene carbon-carbon bonds. Tetrakis(2-hydroxyphenyl)ethene derivatives are designed to promote multiple metal bridging over chelating coordination modes. The ligand is synthesized from anisole or 4-tert-butylanisole in four steps via the 2,2'-dimethoxybenzophenone hydrazones 4a,b. The sterically hindered ortho-substituted tetraphenylethylene core is produced in high yield by acid-catalyzed decomposition of the corresponding diaryl diazomethane prepared in situ by oxidation of the hydrazone using nickel peroxide. Deprotection of the methyl ethers using boron tribromide gives tetrakis(2-hydroxyphenyl)ethene (1a), characterized by X-ray crystallography, and tetrakis(5-tert-butyl-2-hydroxyphenyl)ethene (1b). Sterically isolating substituents in the 3-position can be installed via Claisen rearrangement/hydrogenation, providing tetrakis(3-n-propyl-2-hydroxyphenyl)ethene (6) efficiently. To illustrate potential applications of this unprecedented ligand class, two coordination complexes are reported, including tetrakis(2-diethylaluminoxyphenyl)ethene (8), a structurally robust eight-membered-ring aluminum/oxygen crown complex characterized both in solution and in the solid state.