The U-shaped, multifunctionalized tetraetheno-bridged dicyclopentab,ianthracenediol 10 was synthesized to serve as a platform molecule. The molecule was prepared from the Diels−Alder adduct 5a of tricycloundecatriene 3 and bicyclo2.2.2octene-fused p-benzoquinone 4. Functionalization of 10 to construct crab-like molecules was achieved via the base-promoted bis-O-alkylation of two endo-oriented hydroxyl groups at termini in 10 with the following alkyl halides:  allyl, propagyl, and benzyl bromides; 1-bromo- and 1-iodo-4-(bromomethyl)benzene; 9-(bromomethyl)anthracene; 1-(bromomethyl)pyrene; and isomeric bromomethylpyridines. Single-crystal X-ray structures were obtained for bis-phenyl (21) and bis-pyrenyl (25) crabs, and for the silver(I) complex (32 and 33) crabs. The silver(I) complex 32 from bis-o-pyridyl crab 30 is a 2+2 dimeric dimetallocyclophane, and 33 from bis-m-pyridyl crab 29 is a 1+1 metallo-bridged cyclophane. The self-assembled intramolecular π-stacking of pyrenyl rings in 25 with an interplanar distance of 3.40 Å and the consequent π−π interactions were revealed by the X-ray crystal structure and its luminescence property.