The X-ray crystal structure of 2-hydroxy-2′-(1,4-bisoxo-6-hexanol)-1,1′-biphenyl, 3, is presented. This molecule crystallizes in the monoclinic space group P21/n (a = 9.440(2), b = 12.679(3), c = 11.679(3) Å; β = 94.60(2)°; V = 1382.5(5) Å3; Z = 4). One of the unique features of the X-ray structure of 3 is the intramolecular hydrogen bonding. The hydrogens of the phenolic and hydroxy groups occupies bridging positions via hydrogen bonding to an ether oxygen (O1) and a phenolic oxygen (O4), respectively. This hydrogen bonding does not affect the interplanar angle between phenyl rings (49.34°), which is in the range expected for ortho-disubstituted biphenyl compounds. The hydrogen bonding of this type explains why it is difficult to alkylate both phenoxy groups of 2,2′-biphenol with tetrahydropyranyl protected 2-(2′-chloroethoxy)ethanol.