A　series　of　novel　ferrocene-based　benzimidazolium　receptors　4-7　were　designed　and　structurally　characterized,　their　crystal　structures　revealed　that　these　receptors　were　capable　of　incorporating　anions　such　as　PF6　-　and　Br-　and　that　the　molecules　were　linked　by　C-H···X　hydrogen　bonds.　The　anion　binding　studies　were　carried　out　using　various　techniques　including　electrochemistry　(CV　and　SWV),　UV-vis　and　1H　NMR　spectroscopy.　Electrochemical　behavior　indicated　that　all　the　receptors　displayed　rather　strong　electrochemical　sensing　properties　for　F-　in　CH3CN.　For　receptors　6　and　7,　obvious　absorption　changes　were　observed　when　F-　was　added　in　CH　3CN　on　the　UV-vis　spectra.　1H　NMR　titrations　demonstrated　that　all　the　receptors　could　bind　anions　through　(C-H)　+···X-　hydrogen　bonds　forming　1:1　stoichiometric　complexes　and　have　good　fluoride　binding　ability　in　DMSO-d　6.　The　anion　binding　studies　indicated　that　receptors　6　and　7　comprised　of　the　ferrocene-based　benzimidazolium　fragment　and　conjugated　group　showing　better　affinity　for　F-　than　receptors　4　and　5.　©　2014　Elsevier　B.V.　All　rights　reserved.