Dual hydrogen bonding intramolecular bridge pivoted by fluoro group for 1,2-bis(2-fluorophenyl)-3,8-dimethoxyacenaphthenediol in solution is ascertained as simultaneous contribution of mutual fluoro group demonstrated by tangible through-space-couplings in H-1 and F-19 NMR. The shared fluorine atom inside non-coplanarly accumulated aromatic rings molecule adopts quite adequate position free from interfering solvation to interact with two intramolecular hydrogen atoms prior to stronger hydrogen-accepting oxygen atoms nearby so that essentially weak fluorine-concerning non-classical and classical hydrogen bonds fix reinforcingly intramolecular spatial organization.